A photothermal glass and a preparation method thereof

Abstract

The application discloses a kind of photothermal glass and preparation method thereof, it is related to photothermal glass technical field, including main body glass and trace additive;Main body glass includes the following components according to mass percentage:Si O2 58.8~63.4%;A l2O3 12.4~14.6%;Na2O 9.8~13.6%;K2O 4.6~6.8%;MgO 5.6~7.4%;ZrO2 0.6~1.2%;B2O3 0~0.3%;And Fe2O3<0.01%;Trace additive is one or more in CaO, SrO, BaO, ZnO.The trace additive (calcium oxide, barium oxide, strontium oxide, zinc oxide) in the application can also promote the melting of glass raw materials.The photothermal glass prepared by the application has a thermal stability greater than 210℃, an acid resistance level of H1, and an alkali resistance level of A1.

Description

Technical Field

[0001] This invention relates to the field of photothermal glass technology, and more specifically to the field of photothermal glass and its preparation method. Background Technology

[0002] Concentrated solar power (CSP) is a method of generating electricity by converting solar energy into heat energy, and then into electricity. In recent years, the CSP industry has entered a period of rapid development due to its advantages such as being clean and pollution-free, sustainable, widely distributed, and having a large total capacity. The heliostat, as the core component of CSP, mainly functions to reflect sunlight, and the reflector is the core component of the heliostat, made of solar thermal glass.

[0003] The quality of the solar thermal glass directly affects the performance of the reflector and is a necessary foundation for the normal operation of a solar thermal power plant. Compared with other types of glass, solar thermal glass has higher requirements in terms of transmittance, mechanical strength, corrosion resistance, and resistance to thermal shock. Existing patents disclose the following technologies:

[0004] Patent publication number CN114656140A, entitled "A Solar Ultra-White Float Photothermal Glass," discloses the following: A solar ultra-white float photothermal glass comprises the following raw materials in the indicated weight ratios: SiO2: 68wt%–75wt%; Al2O3: 0.3wt%–2.0wt%; Na2O: 12wt%–15.5wt%; K2O: 0wt%–2wt%; CaO: 5wt%–11wt%; Sb2O3: 0.05wt%–0.5wt%; MgO: 1wt%–5wt%; Li2O: 0.1wt%–2.0wt%; Fe2O3 < 0.01wt%.

[0005] Patent publication number CN112521005A, entitled "A Method for Improving the Quality of Float Glass Produced by the Float Process," discloses the following: A method for improving the quality of float glass produced by the float process involves adding a composite clarifying agent to the float glass batch, melting the uniformly mixed raw materials in a melting furnace, and using a bubbling device inside the furnace. The molten glass is then vertically stirred at the neck of the furnace to form a clear and homogenized glass melt for the production of float glass. This invention controls the clarification process of float glass by combining a composite clarifying agent, the glass melting atmosphere, the bubbling process, and the stirring process, thereby reducing microbubbles in the float glass and improving product quality.

[0006] Currently, the aforementioned patents and existing photothermal glass exhibit poor thermal stability and chemical resistance. Summary of the Invention

[0007] The purpose of this invention is to address the poor thermal stability and chemical resistance of existing photothermal glass by providing a photothermal glass and its preparation method.

[0008] To achieve the above objectives, the present invention specifically adopts the following technical solution:

[0009] One aspect of the present invention provides a photothermal glass method, comprising a main glass and trace additives;

[0010] The main glass comprises the following components by weight percentage:

[0011] SiO2 58.8–63.4%;

[0012] Al2O3 12.4–14.6%;

[0013] Na₂O 9.8–13.6%;

[0014] K2O 4.6-6.8%;

[0015] MgO 5.6–7.4%;

[0016] ZrO2 0.6–1.2%;

[0017] B2O3 0–0.3%; and

[0018] Fe2O3 < 0.01%;

[0019] The trace additives are one or more of CaO, SrO, BaO, and ZnO.

[0020] Specifically, solar thermal glass must be designed to withstand various harsh outdoor weather conditions, including extreme cold and heat, for many years. Therefore, it must possess excellent weather resistance, mechanical strength, and chemical stability. This solution incorporates a certain amount of silicon dioxide, aluminum oxide, and zirconium oxide into the glass composition. Simultaneously, the melting process must be carefully considered. Excessive amounts of refractory materials in the formula can lead to defects such as stones, nodules, and bubbles during melting. Excessively high melting temperatures are also detrimental to forming. Therefore, a certain proportion of fluxing alkali metal oxides, sodium oxide and potassium oxide, are added. However, excessive amounts of sodium oxide and potassium oxide can reduce the glass's thermal stability and weather resistance.

[0021] In addition, trace additives (calcium oxide, barium oxide, strontium oxide, zinc oxide) can also promote the melting of glass raw materials.

[0022] In addition, the photothermal glass has a thermal stability greater than 210℃, an acid resistance rating of H1, and an alkali resistance rating of A1. This product can be applied in fields such as solar energy, automobiles, electronic equipment, architectural windows, and photovoltaics.

[0023] In one implementation, A is set to SiO2 + Al2O3 + ZrO2, B is set to Na2O + K2O, and the ratio of 4.0 < A / B < 5.0 is controlled.

[0024] Specifically, in this scheme, A = SiO2 + Al2O3 + ZrO2 and B = Na2O + K2O, and controlling the ratio of 4.0 < A / B < 5.0 is beneficial for the melting and forming of photothermal glass, and can also improve the mechanical strength, weather resistance and chemical stability of photothermal glass.

[0025] In one embodiment, the trace additive comprises, by mass percentage, the following components: CaO 0.001–0.2% and / or SrO 0.001–0.2% and / or BaO 0.001–0.2% and / or ZnO 0.001–0.2%.

[0026] Specifically, CaO (calcium oxide) is an alkaline earth metal oxide that can enhance the physical properties of glass and improve its optical performance. Adding an appropriate amount of calcium oxide to glass can also enhance its hardness and heat resistance, but adding too much will increase the glass's tendency to crystallize.

[0027] Barium oxide (BaO) is a commonly used glass additive. Adding barium oxide can improve the heat resistance of glass. Because barium ions have a large radius, they easily dissolve in the melt during melting, forming a denser network structure, thus making the glass more compact and heat-resistant. At the same time, barium oxide can also increase the hardness of glass. During the melting process, barium oxide can promote the redistribution of other ions in the glass, thereby forming new chemical bonds and increasing the glass's hardness.

[0028] SrO (strontium oxide) is an alkaline earth metal oxide. When added in appropriate amounts, it can lower the melting point of glass, increase its softening point, improve its thermal shock resistance and heat resistance, and make the glass stronger and more durable.

[0029] Zinc oxide (ZnO) is an important glass additive that can improve the heat resistance and chemical stability of glass, while reducing scratches and stains on the glass surface.

[0030] In one implementation, RO is set to CaO + SrO + BaO + ZnO, and the content of RO is controlled to be 0.001% ≤ 0.30% and 0.01 ≤ RO / MgO ≤ 0.05.

[0031] Specifically, the thermal stability of the photothermal glass was improved by combining appropriate trace additives with the main glass composition, while the ratio of the additives to magnesium oxide was controlled at 0.01≤RO / MgO≤0.05 to achieve the best results.

[0032] In one embodiment, the photothermal glass comprises the following components by mass percentage: SiO2 59.2%, Al2O3 14.3%, Na2O 11.8%, K2O 6.4%, MgO 6.8%, ZrO2 1.2%, B2O3 0.19%, Fe2O3 0.0085%, and CaO 0.1%;

[0033] Of these, A accounted for 74.7%, B accounted for 18.2%, the A / B ratio was 4.1, RO accounted for 0.10%, and the RO / MgO ratio was 0.01.

[0034] In one embodiment, the photothermal glass comprises the following components by mass percentage: SiO2 59.8%, Al2O3 13.5%, Na2O 12.0%, K2O 6.1%, MgO 7.4%, ZrO2 0.9%, B2O3 0.14%, Fe2O3 0.0092%, BaO 0.09%, and ZnO 0.06%;

[0035] Of these, A accounted for 74.2%, B accounted for 18.1%, the A / B ratio was 4.1, RO accounted for 0.15%, and the RO / MgO ratio was 0.02.

[0036] In one embodiment, the photothermal glass comprises the following components by mass percentage: SiO2 61.4%, Al2O3 14.0%, Na2O 9.8%, K2O 6.3%, MgO 7.1%, ZrO2 1.0%, B2O3 0.21%, Fe2O3 0.0088%, and SrO 0.18%;

[0037] Of these, A accounted for 76.4%, B accounted for 16.1%, the A / B ratio was 4.7, RO accounted for 0.18%, and the RO / MgO ratio was 0.03.

[0038] In one embodiment, the photothermal glass comprises the following components by mass percentage: SiO2 60.7%, Al2O3 14.6%, Na2O 12.2%, K2O 5.7%, MgO 5.9%, ZrO2 0.6%, B2O3 0.10%, Fe2O3 0.0086%, CaO 0.05%, and BaO 0.10%.

[0039] Of these, A accounted for 75.9%, B accounted for 17.9%, the A / B ratio was 4.2, RO accounted for 0.15%, and the RO / MgO ratio was 0.03.

[0040] In one embodiment, the photothermal glass comprises the following components by mass percentage: SiO2 62.2%, Al2O3 12.6%, Na2O 13.6%, K2O 4.6%, MgO 6.0%, ZrO2 0.7%, B2O3 0.15%, Fe2O3 0.0093%, and ZnO 0.14%;

[0041] Of these, A accounted for 75.5%, B accounted for 18.2%, the A / B ratio was 4.1, RO accounted for 0.14%, and the RO / MgO ratio was 0.02.

[0042] Another aspect of the present invention provides a method for preparing photothermal glass, using the aforementioned photothermal glass, comprising the following steps:

[0043] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0044] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0045] The beneficial effects of this invention are as follows:

[0046] This invention, through the design of the main glass formulation, simultaneously adds a small amount of trace oxides. The trace additives (calcium oxide, barium oxide, strontium oxide, zinc oxide) can also promote the melting of glass raw materials, improve the thermal stability and chemical resistance of the glass, and make the glass quality superior to the glass currently used in mainstream solar thermal power generation applications. Detailed Implementation

[0047] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0048] Example 1

[0049] A photothermal glass comprises the following components by mass percentage: SiO2 59.2%, Al2O3 14.3%, Na2O 11.8%, K2O 6.4%, MgO 6.8%, ZrO2 1.2%, B2O3 0.19%, Fe2O3 0.0085%, and CaO 0.1%;

[0050] Among them, A(SiO2+Al2O3+ZrO2) accounted for 74.7%, B(Na2O+K2O) accounted for 18.2%, A / B was 4.1, RO(CaO+SrO+BaO+ZnO) accounted for 0.10%, and RO / MgO was 0.01.

[0051] The preparation method of this photothermal glass is as follows:

[0052] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0053] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0054] Example 2

[0055] A photothermal glass comprises the following components by mass percentage: SiO2 59.8%, Al2O3 13.5%, Na2O 12.0%, K2O 6.1%, MgO 7.4%, ZrO2 0.9%, B2O3 0.14%, Fe2O3 0.0092%, BaO 0.09%, and ZnO 0.06%.

[0056] Of these, A accounted for 74.2%, B accounted for 18.1%, the A / B ratio was 4.1, RO accounted for 0.15%, and the RO / MgO ratio was 0.02.

[0057] The preparation method of this photothermal glass is as follows:

[0058] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0059] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0060] Example 3

[0061] A photothermal glass comprises the following components by mass percentage: SiO2 61.4%, Al2O3 14.0%, Na2O 9.8%, K2O 6.3%, MgO 7.1%, ZrO2 1.0%, B2O3 0.21%, Fe2O3 0.0088%, and SrO 0.18%.

[0062] Of these, A accounted for 76.4%, B accounted for 16.1%, the A / B ratio was 4.7, RO accounted for 0.18%, and the RO / MgO ratio was 0.03.

[0063] The preparation method of this photothermal glass is as follows:

[0064] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0065] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0066] Example 4

[0067] A photothermal glass comprises the following components by mass percentage: SiO2 60.7%, Al2O3 14.6%, Na2O 12.2%, K2O 5.7%, MgO 5.9%, ZrO2 0.6%, B2O3 0.10%, Fe2O3 0.0086%, CaO 0.05%, and BaO 0.10%.

[0068] Of these, A accounted for 75.9%, B accounted for 17.9%, the A / B ratio was 4.2, RO accounted for 0.15%, and the RO / MgO ratio was 0.03.

[0069] The preparation method of this photothermal glass is as follows:

[0070] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0071] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0072] Example 5

[0073] A photothermal glass comprises the following components by mass percentage: SiO2 62.2%, Al2O3 12.6%, Na2O 13.6%, K2O 4.6%, MgO 6.0%, ZrO2 0.7%, B2O3 0.15%, Fe2O3 0.0093%, and ZnO 0.14%.

[0074] Of these, A accounted for 75.5%, B accounted for 18.2%, the A / B ratio was 4.1, RO accounted for 0.14%, and the RO / MgO ratio was 0.02.

[0075] The preparation method of this photothermal glass is as follows:

[0076] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0077] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0078] Example 6

[0079] A photothermal glass comprises the following components by mass percentage: SiO2 63.1%, Al2O3 13.4%, Na2O 11.7%, K2O 5.0%, MgO 5.6%, ZrO2 0.8%, B2O3 0.17%, Fe2O3 0.0090%, SrO 0.14%, and ZnO 0.08%.

[0080] Of these, A accounted for 77.3%, B accounted for 16.7%, the A / B ratio was 4.6, RO accounted for 0.22%, and the RO / MgO ratio was 0.04.

[0081] The preparation method of this photothermal glass is as follows:

[0082] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0083] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0084] Comparative Example 1

[0085] A photothermal glass comprises the following components by mass percentage: SiO2 60.2%, Al2O3 11.8%, Na2O 12.7%, K2O 6.2%, MgO 6.8%, ZrO2 1.5%, B2O3 0.34%, Fe2O3 0.0096%, and CaO 0.45%.

[0086] Of these, A accounted for 73.5%, B accounted for 18.9%, the A / B ratio was 3.9, RO accounted for 0.45%, and the RO / MgO ratio was 0.07.

[0087] The preparation method of this photothermal glass is as follows:

[0088] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0089] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0090] Comparative Example 2

[0091] A photothermal glass comprises the following components by mass percentage: SiO2 58.2%, Al2O3 13.4%, Na2O 13.8%, K2O 6.6%, MgO 7.0%, ZrO2 0.6%, B2O3 0.39%, and Fe2O3 0.0108%.

[0092] Of these, A accounted for 72.2%, B accounted for 20.4%, and the A / B ratio was 3.5.

[0093] The preparation method of this photothermal glass is as follows:

[0094] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0095] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0096] Comparative Example 3

[0097] A photothermal glass comprises the following components by mass percentage: SiO2 71.5%, Al2O3 0.6%, Na2O 14.0%, K2O 0.4%, MgO 4.5%, Fe2O3 0.0150%, and CaO 8.98%.

[0098] Of these, A accounted for 72.1%, B accounted for 14.4%, the A / B ratio was 5.0, RO accounted for 8.98%, and the RO / MgO ratio was 2.00.

[0099] The preparation method of this photothermal glass is as follows:

[0100] S1. Weigh the main glass and trace additives as needed, mix them evenly in the mixer, and then transport the mixture to a high-temperature furnace for melting and homogenization via a conveyor belt. The molten glass is then spread out and polished after passing through a tin bath.

[0101] S2. Then, it enters the annealing furnace for precision annealing and cooling, and finally cuts it into light and heat glass plates of the corresponding size.

[0102] Table 1 Performance Comparison of Examples 1 to 6 and Comparative Examples 1 to 3

[0103]

[0104]

[0105] Table 1 compares the performance of Examples 1 to 6 and Comparative Examples 1 to 3. In the comparative examples and examples, the samples used for transmittance, acid resistance, alkali resistance, and three-point bending tests were all 1.0 mm thick photothermal glass sheets. The sample used for thermal stability was a φ4×30 mm glass rod. It can be seen that the photothermal glasses prepared by the formulations and methods used in Examples 1 to 6 have a thermal stability greater than 210℃, an acid resistance rating of H1, and an alkali resistance rating of A1, all of which are superior to the photothermal glasses prepared by Comparative Examples 1 to 3. The excellent thermal stability and acid / alkali resistance enable the application products to operate stably in harsh climatic environments, extending their service life. While improving the thermal stability and acid / alkali resistance of the photothermal glass, the mechanical and optical properties of the photothermal glass are also considered. The three-point bending strength and transmittance of Examples 1 to 6 also maintain a good level.

[0106] The performance of the photothermal glass in the examples and comparative examples was tested using the following standards or instruments:

[0107] 1. The transmittance of the photothermal glass at 550nm was measured using a UV-2450 ultraviolet-visible spectrophotometer;

[0108] 2. Thermal stability (°C) was measured using a vertical tubular electric furnace in accordance with standard SJ / T 11037-1996;

[0109] 3. The acid resistance rating was measured according to standard GB / T 15728-2021;

[0110] 4. The alkali resistance level is measured according to standard GB / T 6580-2021;

[0111] 5. The three-point bending test was conducted using a QJ-211S universal testing machine. The test conditions were: span 80cm, rod diameter 6mm, and pressing speed 10mm / min.

Claims

1. A photothermal glass, characterized by, The main body glass and trace additives are included; The main body glass includes the following components by mass percentage: SiO2 58.8-63.4%; Al2O3 12.4-14.6%; Na2O 9.8-13.6%; K2O 4.6-6.8%; MgO 5.6-7.4%; ZrO2 0.6-1.2%; B2O3 0-0.3%; and Fe2O3 <0.01%; The trace additives are one or more of CaO, SrO, BaO and ZnO; A=SiO2+Al2O3+ZrO2, B=Na2O+K2O, and 4.0 The trace additives include the following components by mass percentage: CaO 0.001-0.2%, and / or SrO 0.001-0.2%, and / or BaO 0.001-0.2%, and / or ZnO 0.001-0.2%; RO=CaO+SrO+BaO+ZnO, and 0.001%≤RO≤0.30%, 0.01≤RO / MgO≤0.

05.

2. A photothermal glass according to claim 1, characterised in that The main body glass includes the following components by mass percentage: SiO2 59.2%, Al2O3 14.3%, Na2O 11.8%, K2O 6.4%, MgO 6.8%, ZrO2 1.2%, B2O3 0.19%, Fe2O3 0.0085%, CaO 0.1%; A accounts for 74.7%, B accounts for 18.2%, A / B is 4.1, and RO accounts for 0.10%, RO / MgO is 0.

01.

3. A photothermal glass according to claim 1, wherein The main body glass includes the following components by mass percentage: SiO2 59.8%, Al2O3 13.5%, Na2O 12.0%, K2O 6.1%, MgO 7.4%, ZrO2 0.9%, B2O3 0.14%, Fe2O3 0.0092%, BaO 0.09% and ZnO 0.06%; A accounts for 74.2%, B accounts for 18.1%, A / B is 4.1, RO accounts for 0.15%, and RO / MgO is 0.

02.

4. A photothermal glass according to claim 1, wherein The main body glass includes the following components by mass percentage: SiO2 61.4%, Al2O3 14.0%, Na2O 9.8%, K2O 6.3%, MgO 7.1%, ZrO2 1.0%, B2O3 0.21%, Fe2O3 0.0088%, SrO 0.18%; A accounts for 76.4%, B accounts for 16.1%, A / B is 4.7, RO accounts for 0.18%, and RO / MgO is 0.

03.

5. A photothermal glass according to claim 1, wherein The main body glass includes the following components by mass percentage: SiO2 60.7%, Al2O3 14.6%, Na2O 12.2%, K2O 5.7%, MgO 5.9%, ZrO2 0.6%, B2O3 0.10%, Fe2O3 0.0086%, CaO 0.05%, BaO 0.10%; Among them, A accounts for 75.9%, B accounts for 17.9%, A / B is 4.2, RO accounts for 0.15%, RO / MgO is 0.

03.

6. A photothermal glass according to claim 1, wherein According to mass percentage, the following components are included: SiO2 62.2%, Al2O3 12.6%, Na2O 13.6%, K2O 4.6%, MgO 6.0%, ZrO2 0.7%, B2O3 0.15%, Fe2O3 0.0093%, ZnO 0.14%; Among them, A accounts for 75.5%, B accounts for 18.2%, A / B is 4.1, RO accounts for 0.14%, RO / MgO is 0.

02.

7. A method for the production of a photothermal glass using a photothermal glass according to any one of claims 1 to 6, characterized in that, The method comprises the following steps: S1, the main glass and trace additives are weighed according to the needs, mixed uniformly in a mixer, and the mixed material is transmitted to a kiln through a transmission belt for melting and homogenization, the molten glass liquid is flattened and polished after passing through a tin tank; S2, then enters an annealing kiln for precision annealing and cooling, and finally is cut into corresponding size photothermal glass plates.

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