Float method ultra-thin photo-thermal electronic glass and its preparation method

Abstract

The application discloses a kind of float method ultra-thin photo-thermal electronic glass and preparation method thereof, belong to electronic glass technical field.Its technical scheme is: including the following mass percentage component: SiO2 50-60%, Al2O3 9-13%, B2O3 8-10%, CaO 4-6%, MgO 0.02-0.05%, SrO 5-8%, ZnO 0.2-0.6%, BaO 2-4%, NaF 3-5%, KBr 1-3%, SnO2 0.1-0.3%, Sb2O3 0.5-1%, La2O3 0.5-1%, Y2O3 0.5-1%, Cu 3-5%.The float method ultra-thin photo-thermal electronic glass prepared by the application has less apparent defect, and has excellent thermal performance, electrical performance, mechanical performance and chemical performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic glass, in particular to a kind of float ultra-thin photo-thermal electronic glass and preparation method thereof. BACKGROUND

[0002] Energy is an important material basis for human survival and development, and the development and utilization of energy has greatly promoted the development of world economy and human society. With the rapid development of society and economy, the demand for energy is increasing. In order to cope with the urgent energy crisis and realize the sustainable development of economy and society, all countries in the world are developing renewable energy, optimizing energy structure, realizing multi-energy complementation, and ensuring stable energy supply. Compared with other renewable energy, solar energy has more unique advantages. The sun's light and heat spread all over the world, which is the largest energy treasure house for human beings. It is basically not limited by region and geographical location. As long as the sun shines, its light and heat energy can be utilized.

[0003] Solar photovoltaic power generation has good sustainable development, and has become a key component of human energy structure. Therefore, how to more effectively utilize solar photovoltaic power generation has become a research hotspot at home and abroad. Because rare earth ions have multi-level characteristics, they can produce up-conversion or down-conversion luminescence under the excitation of excitation light source. By using this luminescence characteristic, the light energy that cannot be responded by solar cell semiconductor materials can be converted into usable energy, thereby improving the utilization rate of solar energy. Therefore, rare earth doped silicate glass has potential practical application value in solar photovoltaic cells. For example, Chinese invention patent CN110407462A discloses a kind of rare earth doped silicate glass and its preparation method and application. The glass is prepared from the following molar percentage of raw materials: SiO2: 50-65mol%; B2O3: 5-15mol%; CaCO3: 15-30mol%; Na2CO3: 3-8mol%; R2O3: 3-8mol%; wherein, R2O3 is one or several of Bi2O3, Er2O3 and Tm2O3. The patent uses boron oxide to replace the commonly used aluminum oxide in the prior art; because boron and aluminum elements are in the same main group in the periodic table, and the optical basicity of boron oxide is lower than that of aluminum oxide, and the melting point of boron oxide is also much lower than that of aluminum oxide, thereby having obvious advantages in preparation; and by reasonably adjusting the matrix formula, co-doping multiple ions, and increasing the doping ion concentration, an ultra-wide band luminescent material with a simpler preparation method and good luminescent efficiency is obtained.

[0004] The performance requirements of electronic glass are very harsh, so it is of great significance for the development of national energy to prepare a float ultra-thin photo-thermal electronic glass with few apparent defects, excellent thermal, electrical, mechanical and chemical properties. SUMMARY

[0005] The technical problem solved by the present application is to overcome the shortcomings of the prior art and provide a float ultra-thin photo-thermal electronic glass and a preparation method thereof.

[0006] The technical scheme of the present application is:

[0007] In one aspect, the present application provides a float ultra-thin photo-thermal electronic glass, comprising the following components in mass percentage: SiO2 50-60%, Al2O3 9-13%, B2O3 8-10%, CaO 4-6%, MgO 0.02-0.05%, SrO 5-8%, ZnO 0.2-0.6%, BaO 2-4%, NaF 3-5%, KBr 1-3%, SnO2 0.1-0.3%, Sb2O3 0.5-1%, La2O3 0.5-1%, Y2O3 0.5-1%, Cu 3-5%.

[0008] Preferably, the components include the following in mass percentage: SiO2 52%, Al2O3 11.5%, B2O3 8.5%, CaO 4.5%, MgO 0.03%, SrO 7%, ZnO 0.55%, BaO 3.12%, NaF 4.5%, KBr 2%, SnO2 0.2%, Sb2O3 0.7%, La2O3 0.8%, Y2O3 0.6%, Cu 4%.

[0009] SiO2 is an important glass-forming oxide, and the silicon-oxygen structure as the most stable three-dimensional spatial structure in the glass network becomes the skeleton of the glass, making the glass material have high mechanical strength. And SiO2 can improve the thermal stability, chemical stability, softening temperature, heat resistance, hardness, mechanical strength, and viscosity of the glass. Al2O3 is an intermediate oxide of glass. When the molecular ratio of Na2O to Al2O3 is greater than 1, an aluminum-oxygen tetrahedron [AlO4] is formed and constitutes a continuous structural network with a silicon-oxygen tetrahedron [SiO4]; when the molecular ratio of Na2O to Al2O3 is less than 1, an aluminum-oxygen octahedron [AlO6] is formed, which is an external body and is in the hole of the silicon-oxygen structure network.

[0010] Al2O3 is an intermediate oxide, which can exist in two coordination states in the glass structure of the present application. One is to form aluminum-oxygen tetrahedron [AlO4], which can connect with [SiO4] to strengthen the network structure of the glass. The other is to form aluminum-oxygen octahedron [AlO6], which acts as an extra-network modifier in the glass structure and locates in the interspace of the silicon-oxygen network structure. Al2O3 can improve the viscosity, chemical stability, thermal stability, mechanical strength, hardness and refractive index of the glass and reduce the corrosion of the glass to refractory materials.

[0011] B2O3 is a glass network former, which has a melting temperature of only 755°C. In the glass composition of the present application, B2O3 has a relatively low melting temperature, so it is used to reduce the melting temperature of the glass, reduce the high-temperature viscosity of the glass liquid, make it easy to operate and play a role of a fluxing agent. On the other hand, in the case of a high boron content, boron anomaly occurs, and B2O3 exists in two coordination states in the glass, i.e. boron-oxygen triangle [BO3] and boron-oxygen tetrahedron [BO4]. Among them, [BO4] structure can connect with [SiO4] to strengthen the network structure, and [BO3] as a layered structure can reduce the melting temperature of the glass and improve the dielectric properties of the glass. In addition, as a glass network former, B2O3 can reduce the thermal expansion coefficient, density, dielectric constant and dielectric loss of the glass, etc.

[0012] CaO is a network modifier oxide, which plays a role of modifying the glass network, i.e. changing the glass structure to adjust the various properties of the glass, and has a stabilizing effect on the glass. It can improve the chemical resistance and mechanical strength of the product, and also make the batch property of the glass liquid shorter, and when the content is high, it can make the glass brittle. At the same time, MgO is also a network modifier oxide, which is usually used to replace part of CaO in mixed alkali earth, increase the high-temperature viscosity of the glass, improve the thermal stability and chemical resistance of the glass, adjust the industrial properties of the glass and facilitate the glass process operation. SrO can improve the solubility of the glass without increasing the devitrification temperature of the glass. Alkali earth metal ions have the effects of oxidizing bridging oxygen and weakening silicon-oxygen bonds, which is the main reason for reducing the high-temperature viscosity of the glass. When the field strength of the added alkali earth metal ions is large, it will produce accumulation effect, making the glass structure become compact. Alkali earth metal oxides are often used to adjust the batch property of the glass, which is beneficial to the glass production operation. Sr 2+ has a larger ionic radius than Ca 2+ , the ionic field strength and accumulation ability of Sr + are weaker than Ca 2+ . The larger the ionic radius, the greater the attraction to free oxygen, and the smaller the ability to give free oxygen, so the adsorption ability of Sr 2+ to free oxygen is weaker than Ca 2+The strong, easy and oxygen ion combination forms a covalent compound, which has less ability to destroy the glass network structure, so with the replacement of a part of CaO by SrO, the glass network structure is also enhanced to a certain extent, and the decrease of the thermal expansion coefficient of the glass is also promoted, so as to reduce the thermal expansion coefficient of the glass.

[0013] ZnO as an intermediate oxide, in general, takes the zinc-oxygen octahedron [ZnO6] as the network outer oxide, when the free oxygen in the glass is sufficient, the zinc-oxygen tetrahedron [ZnO4] can be formed to enter the structural network of the glass, so that the structure of the glass is more stable. The appropriate amount of ZnO can reduce the thermal expansion coefficient of the glass and increase the refractive index of the glass.

[0014] BaO as the network outer oxide of the glass, appropriate addition can increase the glass material and can accelerate the melting of the glass, and can be used to increase the refractive index of the glass, so that it is more stable at high temperature; BaO can also improve the damage resistance of the glass. In addition, La2O3 is usually used to increase the refractive index of the glass and reduce the dispersion.

[0015] NaF as the main crystallization phase component of the glass; the purpose of introducing KBr is to act as a reducing agent of Cu + , and can ensure that SnO2 exists in part of Sn 2+ , if the glass does not contain Br - or the content of Br - is not appropriate, F - will participate in the formation of the coordination ball of the modifier, the generation of the coordination ball makes the moving ability of F - enhanced, so as to increase the resistivity of the glass.

[0016] SnO2 and Sb2O3 as thermal reducing agents can control the size of CuO clusters. SnO2 acts as an oxidation-reduction fining agent in the chemical composition of the application, and the fining mechanism reaction formula is as follows:

[0017] SnO2→SnO+1 / 2O2

[0018] SnO+1 / 2O2→SnO2

[0019] Among them, the melting point of SnO2 is 2000℃, the melting point of SnO is 1040℃, the boiling point is 1425℃, and at a high temperature of 1640℃, SnO2 can decompose to produce fining gas O2, and the CO2 gas produced by the carbonate dissolved in the glass melt will diffuse into the bubble formed by O2, and the bubble will expand to a large enough size and rise to the surface of the glass, and the gas will be discharged from the glass melt; and SnO can absorb O2 in the residual bubble in the glass melt when the temperature decreases, and SnO2 is formed again, and the oxidation-reduction balance of SnO2 / SnO is achieved to stabilize the gas, so that the bubble defects in the glass melt are gradually reduced.

[0020] The valence of antimony ion in Sb2O3 is different in the glass due to different atmosphere of dissolving process, usually exists in Sb 3+ and Sb 5+ state. Sb2O3 is used together with SnO2 to achieve the best clearing effect, and is also a network former oxide, which can reduce the softening point of the glass, improve its thermal performance, and increase its chemical stability. The chemical stability of the glass depends on its structural characteristics and different oxides, the closer the network structure is connected, the better the chemical stability is. The Sb-O bond is smaller than [SiO4], and the network structure is loose, which increases the thermal conductivity and resistivity of the glass. Sb2O3 is added to the network, but its structure is looser than [SiO4], the addition of Sb2O3 makes [SiO4] change to [SiO6], which changes its coordination number, reduces the density of the glass network, and reduces the density of the glass.

[0021] La2O3 and BaO together can improve the refractive index of the substrate glass. La2O3 is generally a network modifier in the glass network, La 3+ ion has a large ionic radius and a large field strength. La 3+ is located outside the network, and the increase of La2O3 content will cause the transformation of groups in the glass network from tetraborate group → diborate group → metaborate group, which means that [BO4] decreases relatively, and [BO3] increases relatively. La 3+ 's large field strength and ionic radius can attract non-bridging oxygen in the glass, and at the same time has the effect of stabilizing the excess negative charge in the glass network, which helps to maintain the stability of the network structure.

[0022] The decomposition energy of Y2O3 is 1670.5 J / mol, and the single bond energy of Y-O is 209.3 J / mol, which plays a dense role in the network structure of the glass at the interface between the intermediate and the network modifier. Y 3+ ion has a large ionic radius (r = 0.089 nm) and is not easy to form covalent compounds with other anions. When Y2O3 is added to the glass, Y 3+ with a large ionic radius will deform the network structure of the glass to a certain extent, and the deformed network structure is more prone to vibration, which will cause the network structure of the glass to break, increase the silicon oxygen tetrahedron in the glass structure, and reduce the connection degree of the glass network, thereby reducing the thermal expansion coefficient of the glass. Moreover, rare earth ion Y 3+ has a high field strength, which has a certain accumulation effect on the network of the glass, and also makes the network structure of the glass more dense, thereby increasing the resistivity of the glass.

[0023] Cu is a transition metal element, and its outermost electron configuration of the nucleus is 3d 10 4sl Due to the shielding effect of d-electron layer is weak, resulting in its effective charge is greater than the same period of alkali metal elements or alkaline earth elements, so that the ionization energy of Cu subgroup elements is greater than the same period of alkali metal and alkaline earth elements. In addition, Cu chemical properties is not active, belongs to inert element, has outstanding electrical conductivity and thermal conductivity. Cu + 3d orbit is full, so d 10 The electronic structure of the glass system is colorless and increases the transmittance of the glass. In high temperature state, CuO and Sb2O3 occur redox reaction, Sb 3+ Cu 2+ Reduction of Cu + , so that the glass color becomes colorless transparent; Sb 3+ Cu 2+ Reduction of Cu + , the ionic radius is reduced, and it is better to enter the network structure of the glass, and the network density is enhanced. The reaction formula is: 4CuO+Sb2O3→2Cu2O+Sb2O5. Cu 2+ Participate in the network structure of the glass, because the bond strength of Cu-O bond is larger, the bond angle of Si-O-Si bond is smaller, the bond strength is smaller, the structure of the glass is more compact and the thermal expansion coefficient of the glass is reduced.

[0024] On the other hand, the present application provides a preparation method of the above-mentioned float ultra-thin photo-thermal electronic glass, which adopts float production. The specific process is as follows: after the raw materials are reacted, melted, clarified and homogenized, the glass liquid is floated above the molten metal tin liquid through the flow channel connected between the melting furnace and the tin bath. Due to the surface tension, gravity and pulling force, the width and thickness of the glass are controlled by the edge pulling machine to form a glass ribbon, and finally a flat glass panel is obtained and enters the annealing furnace. After annealing, cooling and cutting in the annealing furnace, the finished glass is obtained.

[0025] Mixing: the glass raw materials are sieved according to the particle size requirements, which is to maximize ensure the uniformity of the particle distribution of the mixture. The sieved glass raw materials are weighed according to the glass formula, and then uniformly mixed by a mixing machine to obtain the mixture. The mixture is added into the kiln for melting, and then the glass is clarified and homogenized to remove the bubbles of the glass melt. The temperature of the kiln is controlled during the melting process. Then the molten glass liquid is annealed, and finally the float ultra-thin photo-thermal electronic glass is obtained after the kiln is cooled to room temperature.

[0026] Preferably, after the batch is added into the kiln, it is first melted at 1520-1560 DEG C for 3.5-4.5 h, and after the glass batch is fully reacted to form a glass melt, the glass melt contains a large amount of bubbles, and then the temperature is increased to 1580-1620 DEG C to make the reaction more sufficient, and the temperature is kept for 2.5-3.5 h.

[0027] Preferably, the glass refining homogenization temperature is 1610-1640 DEG C, and the temperature keeping time is 1-1.5 h.

[0028] Preferably, the annealing temperature is 730-770 DEG C, and the temperature keeping time is 1.5-2.5 h.

[0029] Preferably, the mixing time of the components is 4-6 min, and the stirring rate is 800 r / min, and too short or too long mixing time will seriously affect the uniformity of the glass batch.

[0030] Preferably, pure water is added during the mixing of the components, so that the humidity of the batch is 3.5-5% of the humidity of the finished glass, so as to better improve the adsorbability of the batch, so that the batch can maintain high uniformity during the mixing process, so as to avoid that a large amount of fine powder is generated during the transportation of the batch to the kiln head, which affects the overall quality of the glass.

[0031] Preferably, pure water is added during the mixing of the components, so that the humidity of the batch is 3.5-5% of the humidity of the finished glass, so as to better improve the adsorbability of the batch, so that the batch can maintain high uniformity during the mixing process, so as to avoid that a large amount of fine powder is generated during the transportation of the batch to the kiln head, which affects the overall quality of the glass.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] 1. The present application has superior performance different from other substrate glasses by reasonably designing the components of the float ultra-thin photo-thermal electronic glass. 3+ The larger field strength and ion radius can attract non-bridge oxygen in the glass, and at the same time has the effect of stabilizing the excess negative charge in the glass network, which helps to maintain the stability of the network structure. 3+ CuO and Sb2O3 undergo oxidation-reduction reaction, Sb 2+ is reduced to Cu + , so that the color of the glass becomes colorless and transparent, the ion radius is reduced, and the network structure is better enhanced. 2+The network structure of the glass is participated, and the bond angle of Si-O-Si bond is small and the bond strength is small due to the large bond strength of Cu-O bond, the structure of the glass is more compact, and the thermal expansion coefficient of the glass is reduced. Finally, the photothermal photovoltaic electronic substrate glass with high thermal performance, electrical performance, mechanical performance, chemical performance and small apparent defects is prepared.

[0034] 2. The present application adopts float production, and the glass raw materials are sieved according to the particle size requirements, which can maximize ensure the uniformity of the particle distribution of the batch, and realize the full mixing of the batch in the shortest time. A certain amount of pure water is added during the mixing process to maintain the humidity of the batch, so that it reaches 3.5-5% of the total humidity of the glass, so as to better improve the adsorbability of the batch, so that it can maintain high uniformity during the mixing process, so as to avoid the occurrence of more fine powder during the conveying of the batch to the kiln head, which affects the overall quality of the glass. DETAILED DESCRIPTION

[0035] In order to make the person skilled in the art better understand the technical solutions in the present application, the technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application.

[0036] Examples 1-5 and Comparative Examples 1-6

[0037] The 0.7mm thick float ultra-thin photothermal electronic glass batch prepared in Examples 1-5 and Comparative Examples 1-6 is shown in Table 1-2:

[0038] Table 1 Glass batch of Examples 1-5

[0039] Component Example 1 Example 2 Example 3 Example 4 Example 5 SiO2% 52 50 51 54 55 Al203% 11.5 12.5 11 9.5 10 B2O3% 8.5 8 9.5 10 9 CaO % 4.5 6 4 5.5 5 MgO % 0.03 0.02 0.05 0.04 0.02 SrO % 7 5.5 7.5 6 7 ZnO % 0.55 0.48 0.3 0.56 0.3 BaO % 3.12 4 3.5 2 2.33 NaF % 4.5 3 5 4 3.5 KBr % 2 2.5 1.5 2.5 1.5 SnO2 0.2 0.3 0.25 0.3 0.15 Sb203 0.7 0.85 1 0.6 0.9 La2O3 0.8 1 0.95 0.7 0.9 [Y2O3%] 0.6 0.85 0.95 0.8 0.9 Cu % 4 5 3.5 3.5 3.5 Total % 100％ 100％ 100％ 100％ 100％

[0040] Table 2 Glass batch of Comparative Examples 1-6

[0041]

[0042]

[0043] The preparation method of the glass of Examples 1-5 is as follows: after weighing each component, the components are mixed at a stirring speed of 800 r / min for 4-6 min to obtain a batch, and pure water is added during the mixing of the components to make the humidity of the batch 3.5-5% of the total humidity of the glass; the batch is added to a kiln, and first melted at 1520-1560℃ for 3.5-4.5 h, so that the glass batch is fully reacted to form a glass melt; after the glass melting reaction is completed, the glass liquid contains a large amount of bubbles, and then the temperature is increased to 1580-1620℃ to make the reaction more sufficient, and the temperature is kept for 2.5-3.5 h; then the temperature is increased to 1610-1640℃ for glass clarification and homogenization, and the temperature is kept for 1-1.5 h to remove the bubbles in the glass melt; attention is paid to the temperature control of the kiln during the melting process; the molten glass liquid is then annealed at an annealing temperature of 730-770℃ for 1.5-2.5 h, and finally cooled to room temperature along with the kiln to obtain the float ultra-thin photo-thermal electronic glass. The parameter settings of each process in Examples 1-5 are shown in Table 3, and the parameter settings of Comparative Examples 1-6 are the same as those of Example 1.

[0044] Table 3 Parameter settings of each process in the preparation of the glass of Examples 1-5:

[0045]

[0046]

[0047] Thermal expansion performance test of the glass prepared in Examples 1-5 and Comparative Examples 1-6: the thermal expansion coefficient of the glass sample in the temperature range of 20-300℃ is measured by using a Linke L45 / 236 thermal dilatometer, the temperature rising rate is 5℃ / min, and the temperature rising range is 20-300℃. The result measured by the experimental instrument is the average linear thermal expansion coefficient of the glass sample, and then a certain temperature range (T1, T2) is selected, and then the length change (L2-L1) of the glass sample in this temperature range is obtained, so that the thermal expansion coefficient of the glass is:

[0048] α=(L2-L1) / L(T2-T1)+α0;

[0049] In the formula, α: average linear thermal expansion coefficient of the glass sample, / ℃; T2-T1: temperature change, ℃; L2-L1: length change, mm; α0: compensation coefficient of the thermal dilatometer, 6.5×10 -7 / ℃.

[0050] Thermal conductivity test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: In a guarded hot plate apparatus, a one-dimensional steady heat flow similar to that existing in an infinite plane of two parallel isothermal plates is established in a uniform plate-like specimen having parallel surfaces under steady conditions. To ensure that the one-dimensional heat flow is established in the central measuring cell and that the heat flux density is measured accurately, the heating unit should be divided into a central measuring cell and a guard cell surrounding the measuring cell separated by a gap, and sufficient edge insulation or (and) an outer guard jacket is required, especially for apparatus operating well above or below room temperature, which must be provided with an outer guard jacket. By measuring the one-dimensional steady heat flow Q flowing through the measuring cell under steady state, the area S of the measuring cell, and the temperature difference Δt of the cold and hot surfaces of the specimen, the thermal resistance R (R = Δt x S / Q) or the thermal conductivity C (C = 1 / R) of the glass can be calculated.

[0051] Total solar transmittance test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: The Shimadzu UV-2600i ultraviolet-visible spectrophotometer was used for the test, with a resolution of 0.1 nm and a scanning interval of 1 nm / time, and a main wavelength of 510 nm. The test was performed on a 100 mm x 100 mm glass sheet sample.

[0052] Visible light transmittance test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: The Shimadzu UV-2600i ultraviolet-visible spectrophotometer was used for the test, with a resolution of 0.1 nm and a scanning interval of 1 nm / time, and a main wavelength of 510 nm. The test was performed on a 100 mm x 100 mm glass sheet sample.

[0053] Resistivity test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: Based on Ohm's law, a measurement circuit was constructed using a high-temperature insulating container and high-temperature-resistant electrodes and wires. The glass sample was heated to a melt, an alternating current voltage was applied to the glass melt, the current flowing through the glass melt was measured, the resistance value of the glass melt was obtained, and the resistivity of the glass melt was obtained by combining the cross-sectional area and length of the glass melt, with the formula:

[0054] R = U / I, P = (R x S) / L;

[0055] wherein R: resistance of the glass melt, Ω; U: voltage applied to the glass melt, V; I: current flowing through the glass melt, A; P: resistivity of the glass melt, Ω-cm; S: cross-sectional area of the glass melt, cm 2 ; L: length of the glass melt, cm.

[0056] Dielectric constant test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: A defect-free glass sheet sample with a side length of about 20 mm and a thickness of 3 mm was prepared, dried with distilled water and anhydrous ethanol, and coated with a layer of low-temperature silver paste on both sides (the positions of the two sides were coincident), and then placed in a high-temperature furnace and kept at 480°C for 10 min, slowly cooled to room temperature, and then cleaned with anhydrous ethanol. The sample thickness, the surface back silver area (conductive area), and the instrument-measured capacitance were measured during the experiment, and the calculation formula was:

[0057] ε = Cd / ε0S;

[0058] In the formula, ε: dielectric constant, F / m; C: measured capacitance of the sample, F; d: sample thickness, mm; ε0: vacuum dielectric constant, 8.85 x 10 -12 F / m; S: conductive area, mm 2 .

[0059] Hardness test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: The hardness of the glass sample was tested by the Vickers hardness indentation test method, and the hardness calculation formula was:

[0060] Hv = P / A = 1.8544 x P / d 2 ;

[0061] In the formula, Hv: Vickers hardness, kgf / mm 2 ; P: load, N; A: indentation contact area, mm 2 ; d: average distance between two opposite angles of the residual indentation, mm.

[0062] Flexural strength test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: The three-point bending method was used, and a universal testing machine was used for operation. When preparing the sample, the glass was cut into a strip with a length of about 50 mm, a width of about 15 mm, and a thickness of about 5 mm, and then polished to remove bubbles or cracks on the surface of the sample that could cause stress concentration defects, and the calculation formula was:

[0063] P = 3FL / 2bh 2 ;

[0064] In the formula, P: flexural strength of the sample, MPa; F: load of the sample, N; L: support span, mm; b: sample width, mm; h: sample thickness, mm.

[0065] Density test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: The density of the glass was determined by the Archimedes method. First, the annealed glass was prepared into a glass sample with a regular shape, and the prepared glass sample was free of bubbles, stones, and stripes. Then the glass sample was placed in an ultrasonic cleaner and cleaned with anhydrous ethanol for 3 min to remove foreign matter on the surface of the glass. The calculation formula was:

[0066] Pt = ml / ml (m2 - m3) x (P2 - PI) + PI;

[0067] wherein Pt: density of the glass sample at room temperature, g / cm 3 ; ml: mass of the sample in air, g; m2: mass of the sample and the wire in distilled water, g; m3: mass of the wire in distilled water, g; PI: density in air, g / cm 3 ; P2: density in distilled water, g / cm 3 .

[0068] Chemical stability test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: The block method was used to measure the chemical stability of the glass samples. After annealing and cooling, the glass was cut into blocks with a surface area easy to measure, and then the blocks were placed in a prepared acid or base solution. The chemical stability was determined according to the mass difference before and after the erosion and the surface area of the glass block. The surface of the glass was cleaned with distilled water and ethanol before weighing. The acid and base solutions used in the present application were HF solution and NaOH solution, and the specific standards were as follows:

[0069] HF corrosion resistance: the prepared glass sample was placed in 250 mL of 10% HF solution, and eroded at room temperature for 20 min;

[0070] NaOH corrosion resistance: the glass sample was placed in 250 mL of 5% NaOH solution, and eroded in a 95°C constant temperature water bath for 6 h;

[0071] H2O corrosion resistance: after the surface of the glass sample was ground and polished, it was cleaned with anhydrous ethanol, and then placed in 250 mL of distilled water, and eroded in a 95°C constant temperature water bath for 24 h.

[0072] Surface roughness test of the glasses prepared in Examples 1-5 and Comparative Examples 1-6: A glass product with a size of 356 mm x 416 mm was placed on the stylus surface roughness measuring instrument platform. The sample could not be bent, and was placed for 5 min or more to ensure that the sample was consistent with the room temperature. The probe was placed on the sample, and the test probe movement direction was required to be consistent or perpendicular to the sample flow direction. The measurement position was determined, and the starting measurement position was marked for testing.

[0073] The warpage test of the glass prepared in Examples 1-5 and Comparative Examples 1-6: take the glass product with the size of 356 mm x 416 mm, first determine the tin side and the non-tin side of the glass, place the sample on the marble platform for rotation, if it can rotate freely, the upper side is the tin side, and the contact side with the marble platform is the air side, and simultaneously check with the positioning angle in both directions. Lightly place the sample on the marble platform, select the appropriate size of the caliper and insert it into the four corners of the glass sample one by one. The judgment standard: the thickness of the caliper is increased to the maximum value at which the glass sample just does not move, which is the warpage value of the corner, and the maximum measurement value of the four corners is the actual warpage value (the sample depth is <10 mm when the caliper is inserted into the sample corner edge).

[0074] The performance test results of the 0.7 mm thick float ultra-thin photothermal electronic glass prepared in Examples 1-5 and Comparative Examples 1-6 are shown in Tables 4-5:

[0075] Table 4 Performance test results of the float ultra-thin photothermal electronic glass prepared in Examples 1-5

[0076]

[0077]

[0078] Table 5 Performance test results of the float ultra-thin photothermal electronic glass prepared in Comparative Examples 1-6

[0079]

[0080]

[0081] From the data comparison in Tables 4-5, compared with Example 1, the thermal expansion coefficient of the glass prepared in Comparative Example 1 increases, and the bending resistance decreases. This is mainly due to the fact that Sr 2+ has the effect of oxidizing the bridging oxygen and weakening the silicon-oxygen bond, which will produce an accumulation effect, making the glass structure compact. Sr 2+ has a larger ionic radius than Ca 2+ , the ionic field strength and accumulation ability of Sr 2+ are weaker than Ba 2+ , the larger the ionic radius, the greater the attraction to free oxygen, and the smaller the ability to give free oxygen, so Sr 2+ has a stronger ability to adsorb free oxygen than Ba 2+ , and it is easy to combine with oxygen ions to form a covalent compound, so its ability to destroy the glass network structure is smaller, so as SrO gradually replaces BaO, the glass network structure is also enhanced to a certain extent, which promotes the reduction of the thermal expansion coefficient of the glass.

[0082] It can also be seen that the thermal properties of the glass prepared in Comparative Example 2 are decreased compared with those of Example 1, including the decrease of total solar transmittance and visible light transmittance. This is mainly because Sn belongs to the same group as Si in the periodic table, and a small amount of SnO2 exists in the glass in the form of [SnO4], which accelerates the decomposition of SnO2 to produce clear gas O2, making the glass melt more clear during the melting process, and increasing the visible light transmittance and total solar transmittance of the finished glass. At the same time, the glass prepared in Comparative Example 2 has more surface defects than Example 1, mainly because the SnO2 as a thermal reducing agent can gradually reduce the bubble defects in the glass melt, resulting in a decrease in the surface defects of the glass.

[0083] In addition, the thermal conductivity, density and chemical stability of the glass prepared in Comparative Example 3 are decreased compared with those of Example 1. This is mainly because Sb2O3 is a network former oxide, which can improve the thermal properties of the glass, making the network structure more closely connected and the chemical stability better. The Sb-O bond is smaller than [SiO4], which makes the network structure loose, increasing the thermal conductivity and resistivity of the glass. The addition of Sb2O3 changes [SiO4] to [SiO6], changing the coordination number and reducing the density of the glass network. However, the generation of Sb-O bond in the glass can significantly improve the density of the glass.

[0084] Compared with Example 1, the visible light transmittance and chemical stability of the glass prepared in Comparative Example 4 are decreased. This is because La2O3 and BaO work together to improve the visible light transmittance of the substrate glass. La 3+ has a larger ionic radius and a larger field strength. La 3+ is located outside the network, and an increase in the content of La2O3 will cause the transformation of groups in the glass network from tetraborate group to diborate group to metaborate group, which means that [BO4] decreases relatively, while [BO3] increases relatively. La 3+ with a larger field strength and ionic radius can attract non-bridging oxygen in the glass, while also having the effect of stabilizing the excess negative charge in the glass network, which helps to maintain the stability of the network structure and enhance the hardness of the glass.

[0085] Compared with Example 1, the thermal expansion coefficient of the glass prepared in Comparative Example 5 is increased and the resistivity is decreased, which is mainly because Y2O3 added to the glass has a larger ionic radius than Si 3+ , which will cause deformation of the glass network structure to a certain extent, leading to the breaking of the glass network structure, increasing the silicon-oxygen tetrahedron in the glass structure, and reducing the degree of connection of the glass network, thereby reducing the thermal expansion coefficient of the glass. Moreover, the rare earth ion Y 3+ has a high field strength, which has a certain accumulation effect on the glass network, making the glass network structure more closely connected and increasing the resistivity of the glass.

[0086] Compared to Example 1, the glass prepared in Comparative Example 6 exhibited decreased visible light transmittance, resistivity, and dielectric constant, while its coefficient of thermal expansion increased. This is primarily because Cu is a transition metal element, chemically inert, which leads to increased resistivity and enhanced thermal conductivity. + The 3D orbit is completely full, so d 10 The electronic structure of CuO lacks dd transitions, therefore it has no coloring ability, exhibiting colorlessness in this glass system and increasing the glass's transmittance. At high temperatures, CuO and Sb₂O₃ undergo a redox reaction, and Sb₂O₃… 3+ Cu 2+ Reduced to Cu + The reaction equation is 4CuO + Sb₂O₃ → 2Cu₂O + Sb₂O₅; Cu 2+ Cu-O bonds are involved in the network structure of glass. Due to the relatively strong bond strength of Cu-O bonds, the bond angle of Si-O-Si bonds becomes smaller and the bond strength becomes weaker, resulting in a more compact glass structure and a lower coefficient of thermal expansion.

[0087] Comparative Examples 7-8

[0088] The mixing time of the batch materials during the preparation of the 0.7 mm thick float-type ultrathin photothermal electronic glass in Comparative Examples 7-8 is shown in Table 6.

[0089] Table 6 shows the mixing time of the batch materials for comparative examples 7-8: float ultrathin photothermal and electronic glass.

[0090] Comparative Example 7 Comparative Example 8 Batch mixing time (min) 3 8

[0091] Determination of the electrical conductivity of the glasses prepared in Examples 1-5 and Comparative Examples 7-8: The difference in the content of water-soluble salts in the glass batch samples was used as an indicator of batch uniformity. The uniformity of each batch could be determined based on the difference in conductivity of the solutions. The testing method involved taking approximately 10g of the batch material and placing it in an evaporating dish. After taking the sample, the dish was placed in a 105℃ oven for 2 hours to dry the moisture. Afterward, it was placed in a desiccator and cooled to room temperature. 5g of the sample was weighed using a 0.01% balance and placed in a beaker. The sample weight was recorded. 200mL of pure water was added, and the mixture was allowed to stand for 5 minutes. Then, the mixture was stirred on a magnetic stirrer for 5 minutes. After standing for 5 minutes, the conductivity was measured using a conductivity meter, and the data was recorded. The calculation formula is:

[0092]

[0093] In the formula, B: conductivity value after conversion to sample weight, S / m; A: conductivity value, S / m; m: sample weight, g; C: average value of the converted value, S / m; D: standard deviation of the converted value; E: uniformity of the batch, %; n: number of samples.

[0094] The results of the uniformity test of the 0.7 mm thick float ultra-thin photothermal electronic glass frits prepared in Examples 1-5 and Comparative Examples 7-8 are shown in Table 7.

[0095] Table 7 Results of the uniformity test of the glass frits of Examples 1-5 and Comparative Examples 7-8

[0096]

[0097] As can be seen from the data in Table 7, the uniformity of the glass frits of Comparative Example 7 and Comparative Example 8 both decreased compared to Examples 1-5. This is mainly because the mixing time in Comparative Example 7 was too short, which caused the frits to mix unevenly, resulting in the raw materials such as silica sand not being mixed evenly, and also remaining at the bottom of the mixer, which caused the frits to be uneven when transported to the kiln head bin and then into the kiln, resulting in the clumping of refractory silica raw materials, and defects such as waves and stones in the glass. In Comparative Example 8, the mixing time was too long, which easily caused the density of the lighter Sn02, Sb203, La203, Y203raw materials to adhere to the side of the mixer, resulting in a lack of light density raw materials in the frit, which affected the overall performance of the glass.

[0098] Comparative Examples 9-13

[0099] The humidity of the 0.7 mm thick float ultra-thin photothermal electronic glass frits prepared in Comparative Examples 9-13 is shown in Table 8:

[0100] Table 8 Humidity of the float ultra-thin photothermal electronic glass frits of Comparative Examples 9-13

[0101] Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Batch moisture (%) 2.5 3.5 4 5.5 6.5

[0102] The uniformity of the 0.7 mm thick float ultra-thin photothermal electronic glass frits prepared in Comparative Examples 9-13 was measured using the aforementioned method, and the test results are shown in Table 9:

[0103] Table 9 Results of the uniformity test of the glass frits of Comparative Examples 9-13

[0104]

[0105] As can be seen from the comparison of the data in Tables 7 and 9, the glass batch uniformity of Comparative Examples 9-13 is reduced compared to Examples 1-5. This is because controlling the batch to maintain a suitable moisture level facilitates the mixing uniformity of the batch. Adding an appropriate amount of moisture to the batch to make the batch have a suitable moisture level can increase the adhesion of the batch, making it easier for the materials to be mixed uniformly, reducing the stratification and caking of the batch during transportation and in the delivery to the kiln head bin, and reducing the apparent defects of the glass product. A suitable moisture level of the batch can wet the surface of the silica sand, form a water film, and enhance the dissolution adhesion and heat conduction capacity of the cosolvent, promoting the melting of the glass batch. A moderate moisture level of the batch can promote the fining and homogenization of the glass liquid.

[0106] As can be seen from the above experiments, in the production of float ultra-thin photo-thermal electronic glass, the design of the batch and process has an important influence on the forming ability, apparent defects and other comprehensive properties of the glass. The float ultra-thin photo-thermal electronic glass prepared by the present application using SiO2, Al2O3, B2O3, CaO, MgO, SrO, ZnO, BaO, NaF, KBr, SnO2, Sb2O3, La2O3, Y2O3 and Cu as raw materials, adopting a float process and according to a specific batching procedure has excellent performance, and its performance indicators are superior to those of similar glasses, with high resistivity, strong mechanical properties, good chemical stability, small thermal expansion coefficient and small apparent defects, and has a good application prospect.

Claims

1. Float ultrathin photothermal electronic glass, characterized in that, The composition includes the following components by mass percentage: SiO2 50-60%, Al2O3 9-13%, B2O3 8-10%, CaO 4-6%, MgO 0.02-0.05%, SrO 5-8%, ZnO 0.2-0.6%, BaO 2-4%, NaF 3-5%, KBr 1-3%, SnO2 0.1-0.3%, Sb2O3 0.5-1%, La2O3 0.5-1%, Y2O3 0.5-1%, Cu 3-5%; The preparation method of float ultrathin photothermal electronic glass involves weighing each component and mixing them to obtain a batch. The batch is then added to a furnace for melting, followed by glass clarification and homogenization. Subsequently, the molten glass is annealed, and finally cooled to room temperature in the furnace to obtain float ultrathin photothermal electronic glass. Pure water is added during the mixing process to make the moisture content of the batch material 3.5-5% of that of the finished glass.

2. The float ultrathin photothermal electronic glass as described in claim 1, characterized in that, The composition includes the following components by mass percentage: SiO2 52%, Al2O3 11.5%, B2O3 8.5%, CaO 4.5%, MgO 0.03%, SrO 7%, ZnO 0.55%, BaO 3.12%, NaF 4.5%, KBr 2%, SnO2 0.2%, Sb2O3 0.7%, La2O3 0.8%, Y2O3 0.6%, and Cu 4%.

3. The float ultrathin photothermal electronic glass as described in claim 1, characterized in that, After the batch is added to the kiln, it is first melted at 1520-1560℃ for 3.5-4.5 hours, and then heated to 1580-1620℃ and held for 2.5-3.5 hours.

4. The float ultrathin photothermal electronic glass as described in claim 1, characterized in that, The glass clarification and homogenization temperature is 1610-1640℃, and the holding time is 1-1.5h.

5. The float ultrathin photothermal electronic glass as described in claim 1, characterized in that, The annealing temperature is 730-770℃, and the holding time is 1.5-2.5h.

6. The float ultrathin photothermal electronic glass as described in claim 1, characterized in that, The mixing time for each component is 4-6 minutes, and the stirring rate is 800 r / min.

7. The float ultrathin photothermal electronic glass as described in claim 1, characterized in that, Pure water is added during the mixing process to make the moisture content of the batch material 4.5% of the total moisture content of the glass.

Images