CN116282915A - High-temperature-resistant glass, preparation method thereof, glass preform and optical element - Google Patents
High-temperature-resistant glass, preparation method thereof, glass preform and optical element Download PDFInfo
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- CN116282915A CN116282915A CN202310193933.6A CN202310193933A CN116282915A CN 116282915 A CN116282915 A CN 116282915A CN 202310193933 A CN202310193933 A CN 202310193933A CN 116282915 A CN116282915 A CN 116282915A
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- 239000011521 glass Substances 0.000 title claims abstract description 142
- 230000003287 optical effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 229910001018 Cast iron Inorganic materials 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 6
- 239000000156 glass melt Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 description 34
- 238000004321 preservation Methods 0.000 description 21
- 230000007774 longterm Effects 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005520 electrodynamics Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008447 perception Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses high-temperature-resistant glass, a preparation method thereof, a glass prefabricated member and an optical element. In the invention, the cation of the high temperature resistant glass contains 22.50 to 23.25mol percent of Si in terms of the mole percent of the cation 4+ 7.39mol% to 8.02mol% of Al 3+ 7.18mol% to 7.71mol% of Na + 0 to 0.55mol% of K + 0.05mol% to 0.07mol% Sn 4+ 0.06mol% to 0.12mol% Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The anions of the high temperature resistant glass contain 61.23 to 61.60mol percent of O in terms of the mole percent of anions 2‑ . The high-temperature resistant glass material prepared by the invention has far lower melting temperature than quartz glass, and simultaneouslyHas higher softening point temperature and stronger glass stability.
Description
Technical Field
The invention relates to the field of new glass materials, in particular to high-temperature-resistant glass, a preparation method thereof, a glass prefabricated member and an optical element.
Background
In industries such as ceramics and powder metallurgy, it is generally required to provide an observation window for observing the sintering condition in a furnace chamber on a furnace door of a high temperature furnace, and install photographing equipment near the observation window to record the reaction progress of materials in the high temperature furnace in real time. This requires that the lens glass of the photographing apparatus have both excellent visible light transmittance and heat resistance.
As is known, glass is a transparent inorganic nonmetallic material, and the manner of making large-size bulk or flat glass is mainly a "melt-cooling" method, namely: firstly, the glass batch is completely melted, clarified and homogenized at high temperature, and then is prepared through the process steps of molding, annealing and the like. In the known glass systems, quartz glass, owing to its unique glass structure, imparts good thermal shock resistance, often at temperatures of 1100 ℃ to 1200 ℃. However, quartz glass is produced from various pure natural quartz (e.g., crystal, sand, etc.) by high-temperature melting, and the production of quartz glass generally requires extremely high temperatures, up to 2000 ℃ or more, which makes the production cost thereof high. Furthermore, quartz glass can also be produced by synthesis, but such methods have lower production efficiency, resulting in further increase in production cost.
The difficulty in designing such high temperature resistant lens glasses is in two aspects: on the one hand, the glass cannot be deformed at high temperatures around 1000 ℃, which requires that the viscosity of the glass be sufficiently high, i.e. that the expansion softening point temperature should be higher than 1000 ℃; on the other hand, the glass cannot devitrify due to crystallization when kept in a high temperature state for a long period of time, i.e., has strong glass stability.
In addition, devices employing CCD or CMOS image sensors have spectral sensitivity ranging from the visible region to about 1100nm when photographing a color scene. Since the "perception" of color by a CCD or CMOS image sensor is different from that of the human eye, the infrared portions that are detectable by them but undetectable by the human eye must be removed, so that the color of the image is in accordance with the perception of the human eye. Therefore, it is generally necessary to "turn off" the near infrared light, i.e.: the transmittance of near infrared rays is reduced, and the effect of high definition is achieved.
Up to now, there is no report of high temperature resistant glass capable of overcoming the above-mentioned drawbacks.
Disclosure of Invention
The invention provides high-temperature-resistant glass, a preparation method thereof, a glass prefabricated member and an optical element, and aims to overcome the defects of the prior art.
The invention is realized by the following technical scheme:
the cation of the high temperature resistant glass contains 22.50 to 23.25mol percent of Si in terms of cation mole percent 4+ 7.39mol% to 8.02mol% of Al 3+ 7.18mol% to 7.71mol% of Na + 0 to 0.55mol% of K + 0.05mol% to 0.07mol% Sn 4+ 0.06mol% to 0.12mol% Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The anions of the high temperature resistant glass contain 61.23 to 61.60mol percent of O in terms of the mole percent of anions 2- . In the above arrangement, si 4+ Is the main component for forming glass, namely: network former ions, if Si 4+ Below 22.50mol% the glass viscosity is low and crystallization tends to occur when the temperature reaches 1000 ℃, and if above 23.25mol% it is difficult to melt and clarify the glass; al (Al) 3+ Is glass intermediate ion, al 3+ The glass has 4, 5, 6 coordination and proper amount of Al 3+ The content being such that it exists predominantly in 4-coordinate form, if Al 3+ If the viscosity of the glass is lower than 7.39mol%, the viscosity of the glass is lower than 8.02mol%, the glass is difficult to melt, and crystallization tends to occur at high temperature; na (Na) + For lowering the glass melting temperature while acting as an electrodynamic counterion to promote Al in the glass 3+ By [ AlO ] 4 ]In the form of four coordinates, if Na + Below 7.18mol%, the viscosity of the glass becomes too high, na + Above 7.71mol%, glass tends to crystallize at high temperatures; k (K) + For lowering the glass melting temperature while acting as an electrodynamic counterion to promote Al in the glass 3+ By [ AlO ] 4 ]In the form of tetradentate, but if K + Above 0.55mol%, glass tends to crystallize at high temperatures; sn (Sn) 4+ Plays a role in clarifying in the glass melting process, is favorable for discharging bubbles in the glass melt, and is suitable for the glass melt if Sn 4+ Below 0.05mol%, the refining time is longer, sn 4+ Above 0.07mol%, glass tends to crystallize at high temperatures; cu (Cu) 2+ In the glass, act as a near infrared absorber, if Cu 2+ If the content is less than 0.06mol%, the effect of near infrared absorption is poor, and Cu 2+ Above 0.12mol%, glass tends to crystallize at high temperatures; o (O) 2- Is mainly present in oxide glass [ SiO ] 4 ]Tetrahedra and [ AlO ] 4 ]In tetrahedra, namely: mainly in the form of "bridging oxygen", in the system glass when O 2- Below 61.23mol%, the glass melt viscosity is high and melting is difficult; conversely O 2- If the amount is more than 61.60mol%, the "non-bridging oxygen" content increases, and the glass tends to crystallize at high temperatures.
Preferably Si 4+ The content of (2) is 22.60mol% to 23.10mol%.
Preferably Al 3+ The content of (C) is 7.52mol% to 8.00mol%.
Preferably Na + The content of (C) is 7.45mol% to 7.70mol%.
Preferably, K + The content of (C) is 0.00mol% to 0.32mol%.
Preferably Sn 4+ The content of (C) is 0.06mol% to 0.07mol%.
Preferably Cu 2+ The content of (C) is 0.08mol% to 0.10mol%.
Preferably O 2- The content of (C) is 61.30mol% to 61.52mol%.
A preparation method of high-temperature-resistant glass comprises the following steps: (1) According to the chemical composition, accurately weighing the weight of the corresponding raw materials of each composition, uniformly mixing to prepare a batch, melting and homogenizing the batch in a high-temperature furnace at 1700-1745 ℃; (2) The glass melt obtained in the step (1) is cast in a cast iron mold with a preheating temperature of 800-830 ℃, rapidly transferred into a muffle furnace for annealing for 1-2.5 hours, and then cooled to room temperature.
Preferably, the raw materials used are silica, alumina, sodium carbonate, potassium carbonate, tin dioxide and copper oxide.
A glass preform is made of the high-temperature-resistant glass.
An optical element is manufactured by adopting the high-temperature resistant glass or the glass prefabricated member.
An optical instrument having the above optical element.
The high-temperature-resistant glass material has the advantages of far lower melting temperature than quartz glass, higher expansion softening point temperature and stronger glass stability, and low energy consumption. In addition, the invention relates to a high temperature resistant glass material, which adjusts the relative content of each cation through the glass composition to induce Al 3+ In glass mainly by [ AlO ] 4 ]The existence of coordination forms endows the glass with higher viscosity, and thus inhibits the formation of crystal nuclei from the aspects of thermodynamics and kinetics, namely: crystallization is prevented by inhibiting formation of crystal nuclei of glass, so that the glass cannot be devitrified and devitrified even after long-term heat preservation between 1000 ℃ and an upper limit temperature (namely: expansion softening point temperature), and in addition, the transmittance of the high-temperature resistant glass prepared by the method in a near infrared region of 780-1100nm is low, wherein the transmittance of the high-temperature resistant glass prepared by the method at 800nm can reach 32% at the lowest; the maximum visible light transmittance of the high-temperature-resistant glass prepared in the first to seventh embodiments of the application can reach 88%, and the maximum upper limit temperature for long-term use can reach 1125 ℃; in addition, the high-temperature-resistant glass does not have expensive raw materials in the preparation process, so the high-temperature-resistant glass has the advantages of low cost and easily obtained raw materials.
Drawings
FIG. 1 is an X-ray diffraction chart of the surface of high temperature resistant glass having a thickness of 4.0mm prepared in example I after heat preservation at 1124℃for 1000 hours;
FIG. 2 is an X-ray diffraction pattern of the surface of the high temperature resistant glass having a thickness of 4.0mm prepared in example II after heat preservation at 1122℃for 1000 hours;
FIG. 3 is an X-ray diffraction pattern of the surface of the high temperature resistant glass having a thickness of 4.0mm prepared in example III after heat preservation at 1120℃for 1000 hours;
FIG. 4 is an X-ray diffraction pattern of the surface of the high temperature resistant glass having a thickness of 4.0mm prepared in example IV after heat preservation at 1118℃for 1000 hours;
FIG. 5 is an X-ray diffraction pattern of the surface of the high temperature resistant glass having a thickness of 4.0mm prepared in example five after heat preservation at 1125℃for 1000 hours;
FIG. 6 is an X-ray diffraction chart of the surface of the high temperature resistant glass having a thickness of 4.0mm prepared in example six after heat preservation at 1120℃for 1000 hours;
FIG. 7 is an X-ray diffraction pattern of the surface of the high temperature resistant glass having a thickness of 4.0mm prepared in example seven after heat preservation at 1118℃for 1000 hours;
FIG. 8 is a graph showing the transmittance of high temperature resistant glass having a thickness of 4.0mm prepared in example I after heat preservation at 1124℃for 1000 hours;
FIG. 9 is a graph showing the transmittance of the high temperature resistant glass having a thickness of 4.0mm prepared in example II after heat preservation at 1122℃for 1000 hours;
FIG. 10 is a graph showing the transmittance of high temperature resistant glass having a thickness of 4.0mm prepared in example III after heat preservation at 1120℃for 1000 hours;
FIG. 11 is a graph showing the transmittance of the high temperature resistant glass having a thickness of 4.0mm prepared in example IV after heat preservation at 1118℃for 1000 hours;
FIG. 12 is a graph showing the transmittance of the high temperature resistant glass having a thickness of 4.0mm prepared in example five after heat preservation at 1125℃for 1000 hours;
FIG. 13 is a graph showing the transmittance of high temperature resistant glass having a thickness of 4.0mm prepared in example six after heat preservation at 1120℃for 1000 hours;
FIG. 14 is a graph showing the transmittance of high temperature resistant glass having a thickness of 4.0mm prepared in example seven after heat preservation at 1118℃for 1000 hours.
Detailed Description
The following describes a high temperature resistant glass according to the present invention by way of specific examples, wherein the fifth example is a preferred example. Composition tables (mol%) of the high temperature resistant glasses of examples one to seven are shown in table 1:
TABLE 1
The upper limit temperature in Table 1 means the upper limit temperature (i.e., expansion softening point temperature) for long-term use.
Embodiment one:
according to the composition (cation mol%, anion mol%) of example one shown in Table 1, 339.9 g of silica, 96.1 g of alumina, 93.5 g of sodium carbonate, 8.3 g of potassium carbonate, 2.5 g of tin dioxide and 1.2 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high-temperature ceramic crucible and kept at 1730℃for 5 hours to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 815℃and rapidly transferred to a muffle furnace for heat preservation for 1 hour to eliminate internal stress, and then cooled to room temperature with the furnace, thereby obtaining a high-temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
Embodiment two:
according to the composition (cation mol%, anion mol%) of example II shown in Table 1, 335.3 g of silica, 97.8 g of alumina, 97.2 g of sodium carbonate, 8.5 g of potassium carbonate, 2.4 g of tin dioxide and 1.8 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high-temperature ceramic crucible, kept at 1715℃for 5 hours to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 810℃and rapidly transferred to a muffle furnace for heat preservation for 1 hour to eliminate internal stress, and then cooled to room temperature with the furnace, thereby obtaining a high-temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
Embodiment III:
according to the composition (cation mol%, anion mol%) of example III shown in Table 1, 331.8 g of silica, 99.3 g of alumina, 98.7 g of sodium carbonate, 9.3 g of potassium carbonate, 2.4 g of tin dioxide and 2.4 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high temperature ceramic crucible, kept at 1710℃for 5 hours to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 800℃and rapidly transferred to a muffle furnace for 2 hours to eliminate internal stress, and then cooled to room temperature with the furnace, thereby obtaining a high temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
Embodiment four:
according to the composition (cation mol%, anion mol%) of example four shown in Table 1, 334.6 g of silica, 100.7 g of alumina, 100.6 g of sodium carbonate, 2.1 g of potassium carbonate, 2.3 g of tin dioxide and 2.1 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high-temperature ceramic crucible, heat-preserved for 5 hours at 1700℃to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 800℃and rapidly transferred to a muffle furnace to heat-preserved for 1.5 hours to eliminate internal stress, and then cooled to room temperature with the furnace, thereby obtaining a high-temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
Fifth embodiment:
according to the composition (cation mol%, anion mol%) of example five shown in Table 1, 340.9 g of silicon dioxide, 96.4 g of aluminum oxide, 100.2 g of sodium carbonate, 2.3 g of tin dioxide and 1.8 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high-temperature ceramic crucible, kept at 1745 ℃ for 5 hours to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 830 ℃, rapidly transferred to a muffle furnace for heat preservation for 1 hour to eliminate internal stress, and then cooled to room temperature with the furnace to obtain high-temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
Example six:
according to the composition (cation mol%, anion mol%) of example six shown in Table 1, 344.1 g of silica, 92.8 g of alumina, 96.5 g of sodium carbonate, 3.4 g of potassium carbonate, 2.1 g of tin dioxide and 2.4 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high-temperature ceramic crucible, kept at 1745℃for 5 hours to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 825℃and rapidly transferred to a muffle furnace for 2 hours to eliminate internal stress, and then cooled to room temperature with the furnace, thereby obtaining a high-temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
Embodiment seven:
according to the composition (cation mol%, anion mol%) of example seven shown in Table 1, 343.3 g of silica, 94.5 g of alumina, 98.5 g of sodium carbonate, 2.1 g of potassium carbonate, 1.9 g of tin dioxide and 1.2 g of copper oxide were weighed respectively, these raw materials were thoroughly mixed, then placed in a high-temperature ceramic crucible, kept at 1740℃for 5 hours to melt and homogenize, then cast in a cast iron mold with a preheating temperature of 820℃and rapidly transferred to a muffle furnace for 2.5 hours to eliminate internal stress, and then cooled to room temperature with the furnace, thereby obtaining a high-temperature resistant glass. The high temperature resistant glass was ground and polished to obtain a high temperature resistant glass having a thickness of 4.0mm, and then the high temperature resistant glass having a thickness of 4.0mm was tested, and the test found that the maximum transmittance in the visible light range, the transmittance at 800nm, and the upper limit temperature (i.e., the expansion softening point temperature) for long-term use are shown in table 1.
As can be seen from Table 1, the maximum visible light transmittance of the high temperature resistant glass prepared in examples one to seven of the present application can be up to 88%, the transmittance at 800nm can be up to 32%, and the upper limit temperature for long-term use can be up to 1125 ℃.
In addition, fig. 1 to 7 show X-ray diffraction patterns of the surfaces of the high temperature resistant glasses prepared in examples one to seven respectively after the respective upper limit temperatures for long-term use (i.e., the expansion softening point temperature) were kept for 1000 hours, and as can be seen from fig. 1 to 7, diffraction peaks in fig. 1 to 7 are all dispersed, which means that the high temperature resistant glasses prepared in examples one to seven are still amorphous after the respective upper limit temperatures for long-term use (i.e., the expansion softening point temperature) were kept for 1000 hours, and neither of them is crystallized.
In addition, in order to verify that the high-temperature resistant glasses prepared in examples one to seven are not devitrified and devitrified even after long-term heat preservation at the upper limit temperature for long-term use (i.e., the expansion softening point temperature), the present application specifically keeps the high-temperature resistant glasses prepared in examples one to seven at the upper limit temperature for long-term use for 1000 hours corresponding to each example in table 1, and then detects the transmittance of the high-temperature resistant glasses prepared in examples one to seven after high-temperature preservation for 1000 hours at the upper limit temperature for long-term use corresponding to each example in table 1 by using a spectrophotometer, and the detection results are shown in fig. 8 to 14.
As can be seen from fig. 8 to 14, the high temperature resistant glasses prepared in examples one to seven were almost unchanged in the maximum transmittance of visible light and the transmittance at 800nm after heat preservation at the respective upper limit temperatures for 1000 hours, that is, no decrease in transmittance due to crystallization occurred.
Because the high-temperature resistant glass prepared by the method is kept at the temperature of 1000 ℃ to the upper limit temperature (namely, the expansion softening point temperature) for a long time, the glass can not devitrify and devitrify; moreover, the high-temperature-resistant glass prepared by the method has lower transmittance at 780-1100nm, wherein the transmittance of the high-temperature-resistant glass prepared by the method at 800nm can reach 32%, so that the glass prefabricated member prepared by the high-temperature-resistant glass also has the advantages, and the high-temperature-resistant glass is suitable for long-term use in a high-temperature environment.
The high-temperature-resistant glass can be used for manufacturing glass prefabricated parts and also can be directly used for manufacturing optical elements, and of course, the glass prefabricated parts can also be used for manufacturing optical elements, especially for manufacturing optical elements such as lenses, prisms, reflectors and the like by starting from the high-temperature-resistant glass prepared by the method.
In addition, the application also provides an optical instrument, which is provided with the optical element. Therefore, by using the optical element having the excellent performance on the optical instrument, the applicability of the optical instrument having the optical element to long-term use in a high-temperature environment can be effectively improved. Specifically, the optical device of the present invention may be an optical device that transmits visible light, such as a camera or a video camera.
Claims (10)
1. A high temperature resistant glass, characterized in that: the cation of the high temperature resistant glass contains 22.50 to 23.25mol percent of Si in terms of the mole percent of the cation 4+ 7.39mol% to 8.02mol% of Al 3+ 7.18mol% to 7.71mol% of Na + 0 to 0.55mol% of K + 0.05mol% to 0.07mol% Sn 4+ 0.06mol% to 0.12mol% Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The anions of the high temperature resistant glass contain 61.23 to 61.60mol percent of O in terms of the mole percent of anions 2- 。
2. The high temperature resistant glass according to claim 1, wherein: si (Si) 4+ The content of (2) is 22.60mol% to 23.10mol%.
3. The high temperature resistant glass according to claim 1, wherein: al (Al) 3+ The content of (C) is 7.52mol% to 8.00mol%.
4. The high temperature resistant glass according to claim 1, wherein: k (K) + The content of (C) is 0.00mol% to 0.32mol%.
5. The high temperature resistant glass according to claim 1, wherein: sn (Sn) 4+ The content of (C) is 0.06mol% to 0.07mol%.
6. A preparation method of high temperature resistant glass is characterized in that: the method comprises the following steps: (1) According to the chemical composition, accurately weighing the weight of the corresponding raw materials of each composition, uniformly mixing to prepare a batch, melting and homogenizing the batch in a high-temperature furnace at 1700-1745 ℃; (2) And (3) casting the glass melt obtained in the step (1) into a cast iron mold with the preheating temperature of 800-830 ℃, rapidly transferring into a muffle furnace, annealing for 1-2.5h, and cooling to room temperature along with the furnace.
7. The method for producing a high temperature resistant glass according to claim 6, wherein: the raw materials used are silicon dioxide, aluminum oxide, sodium carbonate, potassium carbonate, tin dioxide and copper oxide.
8. A glass preform, characterized by: the glass preform is made using the high temperature resistant glass of any one of claims 1-5.
9. An optical element, characterized in that: the optical element is made of the high temperature resistant glass as claimed in any one of claims 1 to 5 or the glass preform as claimed in claim 8.
10. An optical instrument, characterized by: the optical instrument having the optical element of claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310193933.6A CN116282915A (en) | 2023-03-03 | 2023-03-03 | High-temperature-resistant glass, preparation method thereof, glass preform and optical element |
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| CN202310193933.6A CN116282915A (en) | 2023-03-03 | 2023-03-03 | High-temperature-resistant glass, preparation method thereof, glass preform and optical element |
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