A glass batch material and glass

Abstract

The application discloses a glass batch and glass, and relates to the technical field of glass, wherein the glass batch comprises a base material, sodium phosphate, wollastonite, limestone, a fining agent and a fluxing agent; the base material comprises a siliceous raw material, an aluminous raw material and a magnesia raw material; in the glass batch, the sum of the weights of the wollastonite and the limestone is m, the weight of the wollastonite is m0, and m0:m is (51-63):100. The glass batch provided by the application can inhibit glass crystallization by using phosphorus oxide and reduce bubbles in the glass.

Description

Technical Field

[0001] This invention relates to the field of glass technology, and in particular to a glass compound and glass. Background Technology

[0002] In the daily production of float glass, a wide variety of surface defects are encountered, with inclusions accounting for over 50% of all defects. Among all inclusions, crystallized stones constitute a particularly significant proportion. With the continuous optimization of float glass production control technology, the number of inclusions introduced from the furnace, those caused by refractory material erosion, and those resulting from ultrafine raw material powders has been significantly reduced. Against this backdrop, the negative impact of inclusions caused by glass crystallization on product quality has become increasingly prominent, becoming a crucial factor restricting glass surface quality. Therefore, developing float glass formulation systems with low crystallization tendency has become a key research direction for improving process level and product competitiveness.

[0003] Introducing small amounts of phosphorus oxide into float glass batches can significantly suppress crystallization. However, in practical industrial applications, it has been found that the introduction of even small amounts of phosphorus oxide into the glass batches easily generates a large number of bubbles, adversely affecting the glass clarification process and leading to an increase in bubble defects in the final glass product. This problem restricts the application of phosphorus oxide in the float glass industry. Summary of the Invention

[0004] The main objective of this invention is to provide a glass batch and glass, which aims to solve the problem of increased bubbles that occur when using phosphorus oxide to prepare float glass.

[0005] To achieve the above objectives, the present invention proposes a glass batch material, which includes base materials, sodium phosphate, wollastonite, limestone, clarifying agent, and flux. The base materials include siliceous raw materials, aluminous raw materials, and magnesium raw materials. In the glass batch material, the sum of the weights of the wollastonite and the limestone is m, and the weight of the wollastonite is m0. Then, m0:m is (51~63):100.

[0006] In one embodiment, the base material includes silica sand, feldspar, and dolomite; and / or, The clarifying agent includes sodium sulfate and carbon powder; and / or, The flux includes soda ash.

[0007] In one embodiment, the clarifying agent comprises sodium sulfate and carbon powder: In the glass batch, the mass percentage of sodium sulfate is 2.75% to 2.95%; and / or, In the glass batch, the carbon powder accounts for 2.89% to 3.09% of the total mass.

[0008] In one embodiment, the chemical composition of the wollastonite, based on the mass percentage of oxides, comprises: 49.7%~50.7% silica; Aluminum oxide 0.73%~0.77%; Calcium oxide 42.8%~43.4%; Magnesium oxide 0.79%~0.83%; Sodium oxide 0.41%~0.43%.

[0009] The present invention also proposes a glass prepared using the glass batch material described above.

[0010] In one embodiment, the chemical composition of the glass includes phosphorus pentoxide, silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide, and potassium oxide.

[0011] In one embodiment, the chemical composition of the glass includes: Phosphorus pentoxide 0.53%~0.97%; Silicon dioxide 71.11%~71.94%; Calcium oxide content: 8.90%~9.40%; Magnesium oxide 2.80%~3.30%; Aluminum oxide 0.80%~1.30%; The combined mass percentage of sodium oxide and potassium oxide is 13.86% to 14.20%.

[0012] In one embodiment, the mass percentage of calcium oxide in the glass is m1, the mass percentage of magnesium oxide in the glass is m2, the mass percentage of aluminum oxide in the glass is m3, the mass percentage of sodium oxide in the glass is m4, and the mass percentage of potassium oxide in the glass is m5. Then: 0.96≤(2m1-m2) / (m3+m4+m5)≤1.05.

[0013] In one embodiment, the upper limit temperature for crystallization of the glass is 962°C to 977°C.

[0014] In one embodiment, the glass has a viscosity of 10. 4 The operating point temperature (Tw) at dPa·s is below 1020℃.

[0015] In the technical solution of this invention, limestone is the calcareous raw material in the glass batch. By replacing part of the limestone with wollastonite and controlling the relative addition of wollastonite to limestone (i.e., m0:m = (51~63):100), an appropriate amount of wollastonite in the glass batch helps to form a stable low-viscosity melting environment. Simultaneously, because 37%~49% of limestone (the weight percentage of limestone in the total weight of limestone and dolomite) is retained, an appropriate number of initial CO2 bubble nuclei are provided. This effectively captures and combines microbubbles generated by sodium phosphate while providing sufficient "carriers" for O2 in the environment. Furthermore, the number of residual bubbles is not excessive, avoiding excessive competition that makes them difficult to expel. In this system, the generation of bubble nuclei, the diffusion of O2, the growth and expulsion of bubbles are re-established into a more efficient dynamic equilibrium. Bubbles can grow uniformly and stably and be expelled at the optimal speed, resulting in better clarification. Therefore, the glass batch provided by this invention can reduce bubbles in the glass while using phosphorus oxide to inhibit glass crystallization. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0017] Figure 1 The heating curve of the high-temperature visual melting test furnace; Figure 2 The image shows the results of the high-temperature visual observation experiment of Comparative Example 1, which was kept at 1450℃ for different times. Figure 3 The image shows the results of the high-temperature visual observation experiment of Comparative Example 2, which was kept at 1450℃ for different times. Figure 4 The experimental results of high-temperature visual observation of Comparative Example 6 after being kept at 1450℃ for different times are shown in the figure. Figure 5 The image shows the results of the high-temperature visual observation experiment of Comparative Example 7, which was kept at 1450℃ for different times. Figure 6 The image shows the results of a high-temperature visual observation experiment of Example 10, where the temperature was kept at 1450℃ for different times.

[0018] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] It should be noted that if the embodiments of the present invention involve directional indicators (such as up, down, left, right, front, back, etc.), the directional indicators are only used to explain the relative positional relationship and movement of the components in a specific posture. If the specific posture changes, the directional indicators will also change accordingly.

[0021] Furthermore, if the embodiments of this invention involve descriptions such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Additionally, the use of "and / or" or "and / or" throughout the text includes three parallel solutions. For example, "A and / or B" includes solution A, solution B, or a solution where both A and B are satisfied simultaneously. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0022] When phosphorus oxide and wollastonite are not introduced into the glass batch, the carbonate raw materials (limestone, dolomite, soda ash, etc.) and fining agents (such as sodium sulfate) together constitute a sophisticated "gas release and transport system." When the batch is heated, the carbonates decompose, releasing a large amount of CO2 gas. This CO2 gas released by the carbonate raw materials forms countless tiny initial microbubbles in the molten glass. These initial microbubbles are crucial; their role is to provide nucleation and attachment sites for the gas subsequently released by the fining agent, acting as "bubble nuclei." Meanwhile, the fining agent (such as sodium sulfate) decomposes at high temperatures (1200~1400°C) to produce oxygen (O2), which diffuses into the existing CO2 microbubbles, causing them to expand in volume and increase buoyancy, thus accelerating their upward movement and discharge. The upward movement of numerous tiny bubbles also provides a microscopic stirring effect on the molten glass, contributing to chemical and thermal homogenization.

[0023] When phosphorus oxide (introduced from sodium phosphate, which decomposes at high temperatures to release phosphorus oxide vapor) is introduced into the glass batch, it forms a low-melting-point phosphosilicate structure with the silicon-oxygen network, reducing the high-temperature viscosity of the glass. Simultaneously, it alters the type of crystal phase and growth kinetics, making crystal formation and growth less efficient, thus inhibiting crystallization. However, phosphorus oxide is unstable at high temperatures, readily decomposing to release oxygen. It also reacts with moisture or other hydrogen-containing substances in the glass to form phosphorus oxyhydroxides (such as HPO3). These compounds volatilize into gases at high temperatures, forming numerous extremely fine and stable microbubbles. Crucially, phosphorus oxide is a highly efficient surfactant that adsorbs onto the gas-liquid interface of the bubbles, significantly reducing the surface tension of the molten glass. This results in smaller initial bubble sizes, greater difficulty in bubble coalescence (due to the surfactant film forming a barrier), and greater stability of the microbubbles, making them less prone to dissolution and disappearance. In other words, when phosphorus oxide is introduced into the glass batch, it not only "creates" microbubbles, but also "protects" these microbubbles and CO2 microbubbles generated by other carbonates in the batch by reducing surface tension, making them a "stubborn population of bubbles" that is difficult to eliminate.

[0024] In view of this, the present invention proposes a glass batch material, which includes base materials, sodium phosphate, wollastonite, limestone, clarifying agent and flux. The base materials include siliceous raw materials, aluminous raw materials and magnesium raw materials. In the glass batch material, the sum of the weights of the wollastonite and the limestone is m, and the weight of the wollastonite is m0. Then the ratio of m0 to m is (51~63):100.

[0025] Wollastonite (CaSiO3) is a silicate mineral. The addition of wollastonite directly introduces network formations (SiO2) and structure modifiers (CaO). Compared to limestone, wollastonite does not have the endothermic decomposition process of limestone, which lowers the high-temperature melting temperature and viscosity of glass. Furthermore, wollastonite provides components through direct melting (CaSiO3 → CaO + SiO2) without releasing any gases. Therefore, in glass batches that already contain phosphorus oxide (sodium phosphate), introducing an appropriate amount of wollastonite to replace limestone can transform wollastonite's role from a simple flux to a "precise bubble population controller" for the entire glass refining system: controlling the weight ratio of wollastonite to the sum of the weights of wollastonite and limestone can improve the glass refining effect.

[0026] When wollastonite is not added, and the glass batch contains limestone and sodium phosphate, sodium phosphate decomposes at high temperatures, releasing phosphorus oxide vapor. Phosphorus oxide is unstable at high temperatures and readily decomposes to release oxygen. Simultaneously, it reacts with moisture or other hydrogen-containing substances in the glass to form phosphorus oxyhydroxides (such as HPO3). These compounds volatilize into gases at high temperatures, forming numerous extremely fine and stable microbubbles. Furthermore, by reducing surface tension, it protects these microbubbles, as well as CO2 microbubbles generated by other carbonates in the batch, making them a stubborn "bubble population" that is difficult to eliminate, thus deteriorating the clarification effect.

[0027] When the amount of wollastonite added is small, i.e., m0:m is less than 51:100, the glass batch contains sodium phosphate and a small amount of wollastonite is introduced to replace limestone. Sodium phosphate and a small amount of wollastonite slightly reduce the viscosity of the glass melt. This low-viscosity environment promotes the rapid rise of a large number of CO2 microbubbles generated by the thermal decomposition of carbonates and microbubbles generated by sodium phosphate. However, because these microbubbles are too small, and the reduction in glass viscosity is insufficient to allow them to overcome surface tension and be effectively discharged, phosphorus oxide, by reducing surface tension, also protects these microbubbles and CO2 microbubbles generated by other carbonates in the batch, making them a stubborn "bubble population" that is difficult to eliminate, thus deteriorating the clarification effect.

[0028] When a large amount of wollastonite is added, i.e., m0:m greater than 63:100, the glass batch contains sodium phosphate and excessively introduces wollastonite to replace limestone, resulting in insufficient limestone retention and a severely inadequate number of CO2 bubble nuclei. Although the viscosity of the glass melt is significantly reduced due to sodium phosphate and a high proportion of wollastonite, the microbubbles generated by sodium phosphate cannot be effectively collected due to the lack of CO2 bubble nuclei as "carriers." For these isolated microbubbles without internal driving force, their discharge rate is still not fast enough under the low viscosity of the glass melt. In addition, the large amount of O2 produced by the decomposition of sodium sulfate cannot find enough "carriers" in the melt, resulting in high supersaturation. These supersaturated O2 can only nucleate explosively and randomly at certain low-energy interfaces (such as refractory materials and unmelted particles), forming a small number of large, uncontrollable bubbles. All of these factors lead to a significant deterioration in the refining process.

[0029] However, when m0:m is (51~63):100, the glass batch contains sodium phosphate and introduces an appropriate amount of wollastonite to replace limestone. The fluxing advantages of sodium phosphate and wollastonite are fully utilized, forming a new, stable, low-viscosity melting environment. Simultaneously, because 37%~49% of limestone is retained (the weight percentage of limestone in the total weight of limestone and dolomite), an optimal number of initial CO2 bubble nuclei are provided. This effectively captures and merges the microbubbles generated by sodium phosphate while providing sufficient "carriers" for O2 in the environment. Furthermore, the number of residual bubbles is not excessive, avoiding excessive competition that makes them difficult to expel. In this system, the generation of bubble nuclei, the diffusion of O2, the growth and expulsion of bubbles are re-established in a more efficient dynamic equilibrium. Bubbles can grow uniformly and stably and be expelled at the optimal rate. At this point, the reduction in surface tension caused by phosphorus oxide is no longer an obstacle, because the bubbles are being effectively removed rather than stabilized, resulting in better clarification. Therefore, the glass batch provided by this invention can reduce bubbles in the glass while using phosphorus oxide to suppress glass crystallization.

[0030] In some embodiments, the base materials include silica sand, feldspar, and dolomite. Silica sand, as the core network form, provides the silica necessary for forming the glass framework, forming the basis of the glass's main structure and chemical stability. Feldspar, as an aluminous raw material, introduces alumina to enhance the glass's chemical stability, mechanical strength, and resistance to crystallization, while also introducing some alkali metal oxides to act as an auxiliary flux. Dolomite, as a magnesium and calcium raw material, introduces magnesium oxide and calcium oxide to adjust the glass's high-temperature viscosity, suppress crystallization tendency, and significantly improve the glass's water resistance and weather resistance.

[0031] In some embodiments, the clarifying agent includes sodium sulfate (Glauber's salt) and carbon powder. Sodium sulfate decomposes at high temperatures to produce gas, which promotes the clarification of the molten glass and removes bubbles. However, sodium sulfate decomposes at a high temperature and incompletely, therefore carbon powder is added as a reducing agent. Carbon powder lowers the decomposition temperature of sodium sulfate through a redox reaction, allowing it to continuously and stably release clarifying gas in the early stages of glass melting, thereby significantly improving clarification efficiency.

[0032] In some embodiments, the flux includes soda ash. Soda ash (sodium carbonate) is the main flux in glass batches. It decomposes rapidly at high temperatures to produce sodium oxide, which reacts with silica in silica sand to form eutectic silicates, thereby significantly reducing the melting temperature of the glass melt, accelerating the melting process, reducing energy consumption, and ensuring that the glass melt has good fluidity for easy forming.

[0033] In some embodiments, the clarifying agent comprises sodium sulfate and carbon powder: the sodium sulfate content in the glass batch is 2.75%~2.95%; the carbon powder content in the glass batch is 2.89%~3.09%. The sodium sulfate and carbon powder content within the above ranges in the glass batch can improve the clarifying effect of the molten glass.

[0034] The sodium sulfate content refers to the percentage of Na₂O introduced by sodium sulfate out of the total Na₂O introduced by both sodium sulfate and soda ash. The mass of Na₂O introduced by sodium sulfate can be expressed by formula G. 硝 ×P 硝 Calculate G using the formula (62 / 142). 硝 P represents the amount of sodium sulfate used in glass batches. 硝 62 represents the purity of Glauber's salt, 62 represents the molar mass of Na₂O, and 142 represents the molar mass of anhydrous Na₂SO₄. The mass of Na₂O introduced by soda ash can be expressed by formula G. 碱 ×P 碱 Calculate G by multiplying by (62 / 106). 碱 P represents the amount of soda ash used in the glass batch. 碱 106 represents the purity of soda ash, and 106 represents the molar mass of Na2CO3.

[0035] Carbon powder content refers to the percentage of fixed carbon introduced by carbon powder to the mass of Na2SO4 introduced by sodium sulfate, i.e., carbon powder content = [(carbon powder amount × fixed carbon content in carbon powder) / (sodium sulfate amount × Na2SO4 content in sodium sulfate)] × 100%.

[0036] In some embodiments, the chemical composition of the wollastonite, by mass percentage of oxides, includes: 0.53%~0.97% phosphorus pentoxide; 49.7%~50.7% silicon dioxide; 0.73%~0.77% aluminum oxide; 42.8%~43.4% calcium oxide; 0.79%~0.83% magnesium oxide; and 0.41%~0.43% sodium oxide.

[0037] The present invention also proposes a glass prepared using the glass batch material described above.

[0038] In some embodiments, the chemical composition of the glass includes phosphorus pentoxide, silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide, and potassium oxide.

[0039] In some embodiments, the chemical composition of the glass, by mass percentage of oxides, includes: 0.53%~0.97% phosphorus pentoxide; 71.11%~71.94% silicon dioxide; 8.90%~9.40% calcium oxide; 2.80%~3.30% magnesium oxide; 0.80%~1.30% aluminum oxide; and the sum of the mass percentages of sodium oxide and potassium oxide is 13.86%~14.20%.

[0040] Silica (SiO2) is the core material constituting the glass network and is mainly introduced from the raw material silica sand. If the SiO2 content is too low, the chemical stability and mechanical strength will decrease. If the SiO2 content is too high, the melting temperature will be too high. It should be noted that in this application, since wollastonite is used to replace part of the limestone, the silica content (mass percentage) can be controlled by adjusting the amount of silica sand added.

[0041] Aluminum oxide (Al2O3) can suppress phase separation in glass and improve its chemical stability and mechanical strength. It is mainly introduced from the raw material feldspar. If the Al2O3 content is too low, the effect of suppressing phase separation and improving chemical stability and mechanical strength will be poor; if the Al2O3 content is too high, the melting temperature and the upper limit of crystallization temperature will be too high.

[0042] Phosphorus pentoxide (P2O5) can reduce the high-temperature viscosity and crystallization temperature of glass, mainly introduced by sodium phosphate. If the P2O5 content is too low, the effect of reducing the high-temperature viscosity and crystallization temperature of glass will not be significant; if the P2O5 content is too high, it will lead to an abnormally high glass crystallization temperature.

[0043] Calcium oxide (CaO) can reduce the high-temperature viscosity of glass, mainly introduced by the raw materials limestone and dolomite. If the CaO content is too low, the reduction in high-temperature viscosity is not significant; if the CaO content is too high, it will shorten the glass's thickness, increase its brittleness, and increase the glass's tendency to crystallize.

[0044] Magnesium oxide (MgO) can reduce the high-temperature viscosity of glass, as well as its tendency and rate of crystallization. It is primarily introduced from the raw material dolomite. If the MgO content is too low, the effect of reducing the high-temperature viscosity, crystallization tendency, and crystallization rate is relatively poor. If the MgO content is too high, it will reduce the glass's thermal stability, chemical stability, and mechanical properties.

[0045] Sodium oxide (Na₂O) and potassium oxide (K₂O) can decrease the high-temperature viscosity of glass and increase its linear thermal expansion coefficient. Na₂O is mainly introduced from the raw material soda ash, while K₂O is mainly introduced from silica sand and albite. In the float glass industry, generally only the total amount of alkali metal oxides (i.e., Na₂O + K₂O) is controlled, not the amount of Na₂O or K₂O alone. If the content of Na₂O + K₂O is too low, the decrease in glass melting temperature is not significant. If the content of Na₂O + K₂O is too high, chemical stability decreases, especially resistance to hydrolysis.

[0046] In some embodiments, the chemical composition of the glass also includes ferric oxide (Fe2O3), which can color the glass and reduce its transmittance in the ultraviolet and visible light bands. Fe2O3 is introduced from impurities in the raw materials. The mass content of Fe2O3, based on the mass percentage of oxides, preferably does not exceed 0.09%.

[0047] It is understood that this application does not limit the amount of other specific materials used in the glass batch, as long as the requirements of the above oxides are met while satisfying the m0:m ratio of (51~63):100. For example, the content of silica can be controlled by adjusting the amount of silica sand added; the content of alumina can be controlled by controlling the amount of feldspar added, etc. This application does not impose any restrictions here.

[0048] Based on the condition that m0:m is (51~63):100, meeting the above requirements for oxides can reduce the glass melting temperature (i.e., reduce the glass viscosity), thereby helping to expel bubbles.

[0049] It should be noted that the amount of each raw material can be calculated based on the target content of each oxide in the glass and the corresponding content of each oxide in each substance.

[0050] To reduce the overall high-temperature viscosity of the glass and stabilize its structure, in some embodiments, the mass percentage of calcium oxide in the glass is m1, the mass percentage of magnesium oxide is m2, the mass percentage of aluminum oxide is m3, the mass percentage of sodium oxide is m4, and the mass percentage of potassium oxide is m5. Therefore: 0.96 ≤ (2m1-m2) / (m3+m4+m5) ≤ 1.05. The macroscopic properties of glass (such as viscosity and clarity) are determined by its microstructure, namely the network composed of [SiO4] and [AlO4] tetrahedra. The role of various oxides is to modify this network structure. (m3+m4+m5) represents the total mass percentage of Al2O3, Na2O, and K2O, indicating the approximate total amount of [AlO4] tetrahedra that need to be stabilized through charge balance in the glass system (because Na...). + and K +(It is the main charge provider); (2m1-m2) is the difference in mass ratio between 2CaO and MgO, which can be approximated as the number of divalent cations remaining after exceeding the balance required for [AlO4], which can be freely used to break the silicon-oxygen network; when the ratio of (2m1-m2) / (m3+m4+m5), that is, the ratio of (2CaO-MgO) / (Al2O3+Na2O+K2O), is controlled within an optimal range, it means that there are enough free Ca 2+ and Mg 2+ These ions, without needing to balance the aluminum-oxygen tetrahedra, can focus entirely on "cutting" the silicon-oxygen network, thus achieving the most effective reduction in viscosity at high temperatures; in addition, the [AlO4] tetrahedra are stably bound by sufficient cations (including Na+). + , K + Ca 2+ Mg 2+ When the glass network is surrounded by charges and in equilibrium, the entire glass network structure becomes more chemically stable at high temperatures. The decrease in the overall viscosity of the molten glass promotes the expulsion of bubbles; the stability of the structure inhibits the formation of new bubbles; this combination of "promotion" and "inhibition" results in a good clarification effect.

[0051] In some embodiments, the upper limit temperature for crystallization of the glass is 962°C to 977°C.

[0052] In some embodiments, the glass has a viscosity of 10. 4 The operating point temperature (Tw) at dPa·s is below 1020℃.

[0053] The technical solution of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0054] Example 1 A glass batching material is provided, comprising 699.2 kg of silica sand, 8.6 kg of feldspar, 137.7 kg of dolomite, 46.7 kg of limestone, 54.8 kg of wollastonite, 220.1 kg of soda ash, 10.5 kg of sodium phosphate, 8.7 kg of mirabilite, and 0.298 kg of carbon powder.

[0055] The above glass batch was placed in a platinum-rhodium crucible and melted at 1450°C for 6 hours to obtain molten glass. The molten glass was then transferred to a tin bath for float glass forming, annealed at 600°C for 2 hours, and then cooled in the furnace to obtain glass.

[0056] The oxide composition of each substance in the above glass batch is shown in Table 1.

[0057] Table 1. Oxide composition and content of various substances in glass batches

[0058] (Table 1 does not include oxides and some impurities that escape in gaseous state during glass preparation) Table 2 Target glass oxide content (glass composition) of Examples 1 to 17 and Comparative Examples 1 to 7

[0059] (In Table 2, M is the value of (2m1-m2) / (m3+m4+m5)) Examples 2 to 17 and Comparative Examples 1 to 7 were prepared using similar procedures to Example 1. The difference between Examples 2 to 17 and Comparative Examples 1 to 7 and Example 1 lies in the composition and / or amount of the glass batch, as detailed in Table 3. The composition and amount of the glass batch in Examples 1 to 16 and Comparative Examples 1 to 8 were calculated based on Tables 1 and 2.

[0060] The difference between Comparative Examples 1-4 and Example 17 lies in the amount of wollastonite used. Compared with Example 17, Comparative Example 1 does not add wollastonite and sodium phosphate, Comparative Example 2 does not add wollastonite but adds sodium phosphate, Comparative Example 3 adds sodium phosphate but the amount of wollastonite added is less, and Comparative Example 4 adds sodium phosphate but the amount of wollastonite added is more. See Table 3 for details.

[0061] Table 3. Composition and dosage of glass batches in Examples 1 to 17 and Comparative Examples 1 to 7

[0062] (The unit for the amount of each substance in Table 3 is kg) Performance testing (1) The high-temperature viscosity curve of glass was tested using an Orton RSV 1600 rotary high-temperature viscometer according to ASTM C-965, where the viscosity was 10. 4 The temperature corresponding to dpa·s is the operating point temperature (Tw), recorded in Table 4.

[0063] (2) The upper limit temperature of crystallization of glass was tested using an Orton GTF-1612SLW-G gradient furnace according to ASTM C-829 and recorded in Table 4.

[0064] (3) A high-temperature visual melting observation experiment was conducted using a GWC-ii-1700 high-temperature visual melting test furnace. A transparent quartz crucible was used as the container in the high-temperature visual melting observation experiment. The batch material was placed in the quartz crucible. During the heating process of the quartz crucible in the high-temperature furnace, a high-definition high-temperature camera was used as the visual acquisition device to collect real-time images and temperatures of the batch material in the quartz crucible. Furthermore, at the clarification temperature, relevant parameters of the bubbles generated in the molten glass were recorded. After image processing software, the reaction, melting, and bubble formation of the glass material during the heating process were clearly and intuitively reflected.

[0065] The specific operation is as follows: After mixing the glass batch material evenly, place the batch material in a quartz crucible, then place the quartz crucible into a high-temperature visual melting test furnace. Start the equipment and conduct a high-temperature visual melting observation experiment. The temperature rise curve settings for the high-temperature visual melting test furnace are as follows: room temperature - 200℃, 5℃ / min; 200-1200℃, 10℃ / min; 1200-1450℃, 5℃ / min; 1450-1450℃, holding for 120 min. The temperature rise curve of the high-temperature visual melting test furnace is attached. Figure 1 The results of high-temperature visual observation experiments on Comparative Examples 1, 2, 6, 7, and 10 at 1450℃ for different times (0 min, 30 min, 60 min, 90 min, 120 min) are as follows: Figures 2-6 As shown in Table 4, the number of residual bubbles in the molten glass after each batch of materials underwent a high-temperature imaging experiment was recorded.

[0066] Table 4 Test results of Examples 1 to 17 and Comparative Examples 1 to 7

[0067] Please refer to Tables 2 to 4 in conjunction with the following: Comparative Example 1 uses a conventional classic float glass formulation as the benchmark system for this invention. All embodiments and other comparative examples of this invention are based on this classic float glass formulation with component adjustments and optimizations. All subsequent performance tests and effect evaluations use Comparative Example 1 as a unified reference benchmark to objectively reflect the technical improvement effect of this invention. Comparative Example 1 has P2O5=0, Q=0, CaO=8.45<8.9, MgO=4>3.3, Na2O+K2O=13.85<13.86, and (2CaO-MgO) / (Al2O3+Na2O+K2O)=0.88<0.95, meaning the chemical composition of the glass in Comparative Example 1 exceeds the requirements of this invention. Comparative Example 1 does not introduce sodium phosphate and wollastonite into its raw materials; instead, limestone is used. Its glass operating temperature (10...) 4The dpa·s value was 1037℃, and the upper limit of crystallization temperature was 993℃; the number of residual bubbles after the high-temperature visual experiment was 10. Details are as follows... Figure 2 As shown.

[0068] The glass chemical composition of Comparative Example 2 is based on Comparative Example 1, with the addition of 0.85% P2O5 (correspondingly subtracting 0.85% SiO2), and Q=0, exceeding the requirements of this invention. Comparative Example 2 only introduced sodium phosphate as a raw material, without introducing wollastonite. The operating temperature of the glass in Comparative Example 2 is (10... 4 The dpa·s) temperature was 1035℃; the upper limit of crystallization temperature was 967℃; however, the number of residual bubbles after the high-temperature visual experiment in Comparative Example 2 was 81. Details are as follows... Figure 3 As shown, this indicates that introducing only P2O5 component into the classic float glass formulation (Comparative Example 1) will worsen the glass melting and clarification effects, leaving a large number of bubbles.

[0069] The chemical composition of the glass in Comparative Example 3 was the same as that in Comparative Example 2, and Q=0.18, exceeding the requirements of this invention. The amount of wollastonite introduced in Comparative Example 3 accounted for 18% of the total amount of limestone and wollastonite. The operating temperature of the glass in Comparative Example 3 was (10... 4 The dpa·s) temperature was 1034℃; the upper limit of crystallization temperature was 966℃; however, the number of residual bubbles after the high-temperature visual experiment in Comparative Example 3 was 75. This indicates that introducing P2O5 components into the classic float glass formulation and then replacing limestone with a small amount of wollastonite does not significantly improve the melting and clarification of the glass.

[0070] The chemical composition of the glass in Comparative Example 4 is the same as that in Comparative Example 2, and the amount of wollastonite introduced in Comparative Example 4 accounts for 79% of the total amount of limestone and wollastonite, exceeding the requirements of this invention. The operating temperature of the glass in Comparative Example 4 is (10...). 4 The dpa·s) temperature was 1032℃; the upper limit of crystallization temperature was 966℃; however, the number of residual bubbles after the high-temperature visual experiment in Comparative Example 4 was 78. This indicates that introducing P2O5 components into the classic float glass formulation and then replacing limestone with excess wollastonite does not significantly improve the melting and clarification of the glass.

[0071] Comparing Comparative Examples 3 and 4 with Comparative Example 2 demonstrates that adding wollastonite can slightly reduce the number of residual bubbles and improve the clarification effect of glass while maintaining the crystallization temperature.

[0072] The chemical composition of the glass in Example 17 is the same as that in Comparative Example 2, except that the amount of wollastonite introduced accounts for 53% of the total amount of limestone and wollastonite, which is within the scope of this application. The operating temperature of the glass in Example 17 is (10...). 4The dpa·s) was 1032℃; the upper limit of crystallization temperature was 967℃; and the number of residual bubbles after the high-temperature visual experiment was 52. This indicates that after introducing P2O5 component into the classic float glass formulation (Comparative Example 2), and replacing limestone with an appropriate amount of wollastonite, the melting and clarification effects of the glass are significantly improved (the number of residual bubbles is reduced from 81 to 52).

[0073] Examples 1-16, based on Example 17, further improved the glass chemical composition. The chemical composition of the glass in Examples 1-16 met the following requirements: phosphorus pentoxide 0.53%-0.97%; silicon dioxide 71.11%-71.94%; calcium oxide 8.90%-9.40%; magnesium oxide 2.80%-3.30%; aluminum oxide 0.80%-1.30%; and the sum of the mass percentages of sodium oxide and potassium oxide 13.86%-14.20%, which further improved the melting and clarification effects of the glass. The upper limit of crystallization temperature of the glass in Examples 1-16 was 962-977℃, which was 16-31℃ lower than that of Comparative Example 1, the classic float glass formulation. The operating temperature (Tw) of the glass in Examples 1-16 was below 1020℃; after completing the high-temperature imaging experiment, the number of residual bubbles was 5-6, which was significantly reduced compared to Example 17. Figure 6 The image shows the results of a high-temperature visual observation experiment conducted in Example 10 at 1450℃ for different durations. Therefore, comparing the data from Examples 1 to 16 and Example 17, it can be seen that when the ratio of m0 to m is within the range of (51~63):100, and the chemical composition of the glass meets the following conditions: phosphorus pentoxide 0.53%~0.97%, silicon dioxide 71.11%~71.94%, calcium oxide 8.90%~9.40%, magnesium oxide 2.80%~3.30%, aluminum oxide 0.80%~1.30%, and the sum of the mass percentages of sodium oxide and potassium oxide is 13.86%~14.20%, the number of residual bubbles at high temperatures can be further reduced, improving the clarification effect of the glass.

[0074] The chemical composition of the glass in Comparative Example 5 was the same as that in Example 10, but wollastonite was not introduced. The operating temperature of the glass in Comparative Example 5 was 10... 4The dpa·s) temperature was 1021℃; the upper limit of crystallization temperature was 977℃; however, the number of residual bubbles after the high-temperature visual experiment of Comparative Example 5 was 23. Compared with Comparative Example 2, the chemical composition of Comparative Example 5 met the following conditions: "phosphorus pentoxide 0.53%~0.97%; silicon dioxide 71.11%~71.94%; calcium oxide 8.90%~9.40%; magnesium oxide 2.80%~3.30%; aluminum oxide 0.80%~1.30%; the sum of the mass percentages of sodium oxide and potassium oxide is 13.86%~14.20%", so the melting temperature was significantly lower than that of Comparative Example 2 (i.e., the glass viscosity was significantly lower), which helped to remove the bubbles; compared with Example 10, Comparative Example 5 did not introduce wollastonite, resulting in poor melting and clarification of the glass, hence the 23 residual bubbles.

[0075] The glass chemical composition of Comparative Example 6 is the same as that of Example 10, but the amount of wollastonite introduced accounts for 81% of the total amount of limestone and wollastonite, indicating an excessive amount of wollastonite. The operating temperature of the glass in Comparative Example 6 is (10...). 4 The dpa·s value was 1019℃; the upper limit of crystallization temperature was 977℃; the number of residual bubbles after the high-temperature visual experiment in Comparative Example 6 was 21, details are as follows. Figure 4 As shown. The chemical composition of Comparative Example 6 satisfies "phosphorus pentoxide 0.53%~0.97%; silicon dioxide 71.11%~71.94%; calcium oxide 8.90%~9.40%; magnesium oxide 2.80%~3.30%; aluminum oxide 0.80%~1.30%; and the sum of the mass percentages of sodium oxide and potassium oxide is 13.86%~14.20%", so the melting temperature is significantly lower (i.e., the glass viscosity is significantly lower), which helps to remove bubbles. Compared with Example 10, Comparative Example 6 introduced an excessive amount of wollastonite, resulting in poor melting and clarification of the glass, hence 21 residual bubbles.

[0076] The glass chemical composition of Comparative Example 7 is the same as that of Example 10, but the amount of wollastonite introduced accounts for 29% of the total amount of limestone and wollastonite, which is too little. The operating temperature of the glass in Comparative Example 7 is (10...). 4 The dpa·s) temperature was 1020℃; the upper limit of crystallization temperature was 976℃; however, the number of residual bubbles after the high-temperature visual experiment in Comparative Example 7 was 20. Details are as follows... Figure 5As shown. The chemical composition of Comparative Example 6 satisfies the following: "Phosphorus pentoxide 0.53%~0.97%; silicon dioxide 71.11%~71.94%; calcium oxide 8.90%~9.40%; magnesium oxide 2.80%~3.30%; aluminum oxide 0.80%~1.30%; and the sum of the mass percentages of sodium oxide and potassium oxide is 13.86%~14.20%", so the melting temperature decreases significantly (i.e., the glass viscosity decreases significantly), which helps to remove bubbles; however, it only introduces a small amount of wollastonite, resulting in poor melting and clarification of the glass, hence 20 bubbles remain.

[0077] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A glass compound, characterized in that, It includes base materials, sodium phosphate, wollastonite, limestone, clarifying agent and flux, wherein the base materials include siliceous raw materials, aluminum raw materials and magnesium raw materials; In the glass batch, the sum of the weights of the wollastonite and the limestone is m, and the weight of the wollastonite is m0, then the ratio of m0 to m is (51~63):

100.

2. The glass batch material as described in claim 1, characterized in that, The base materials include silica sand, feldspar, and dolomite; and / or, The clarifying agent includes sodium sulfate and carbon powder; and / or, The flux includes soda ash.

3. The glass batch material as described in claim 1, characterized in that, The clarifying agent includes sodium sulfate and carbon powder: In the glass batch, the content of sodium sulfate is 2.75%~2.95%; and / or, In the glass batch, the carbon powder content is 2.89%~3.09%.

4. The glass batch material as described in claim 1, characterized in that, The chemical composition of the wollastonite, by mass percentage of oxides, comprises: 49.7%~50.7% silica; Aluminum oxide 0.73%~0.77%; Calcium oxide 42.8%~43.4%; Magnesium oxide 0.79%~0.83%; Sodium oxide 0.41%~0.43%.

5. A type of glass, characterized in that, The glass is prepared using the glass batch material as described in any one of claims 1 to 4.

6. The glass as described in claim 5, characterized in that, The chemical composition of the glass includes phosphorus pentoxide, silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide, and potassium oxide.

7. The glass as claimed in claim 6, characterized in that, The chemical composition of the glass, by mass percentage of oxides, comprises: Phosphorus pentoxide 0.53%~0.97%; Silicon dioxide 71.11%~71.94%; Calcium oxide content: 8.90%~9.40%; Magnesium oxide 2.80%~3.30%; Aluminum oxide 0.80%~1.30%; The combined mass percentage of sodium oxide and potassium oxide is 13.86% to 14.20%.

8. The glass as claimed in claim 6, characterized in that, If the mass percentage of calcium oxide in the glass is m1, the mass percentage of magnesium oxide in the glass is m2, the mass percentage of aluminum oxide in the glass is m3, the mass percentage of sodium oxide in the glass is m4, and the mass percentage of potassium oxide in the glass is m5, then: 0.96≤(2m1-m2) / (m3+m4+m5)≤1.

05.

9. The glass as claimed in claim 6, characterized in that, The upper limit temperature for crystallization of the glass is 962℃~977℃.

10. The glass as claimed in claim 6, characterized in that, The glass has a viscosity of 10. 4 The operating point temperature (Tw) at dPa·s is below 1020℃.

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