CN114163123A - Anti-ultraviolet high-refraction optical glass and preparation method thereof - Google Patents
Anti-ultraviolet high-refraction optical glass and preparation method thereof Download PDFInfo
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- CN114163123A CN114163123A CN202111369166.7A CN202111369166A CN114163123A CN 114163123 A CN114163123 A CN 114163123A CN 202111369166 A CN202111369166 A CN 202111369166A CN 114163123 A CN114163123 A CN 114163123A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000137 annealing Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004327 boric acid Substances 0.000 claims abstract description 16
- 239000006004 Quartz sand Substances 0.000 claims abstract description 13
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 13
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 7
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 93
- 238000003756 stirring Methods 0.000 claims description 82
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 48
- 239000001301 oxygen Substances 0.000 claims description 48
- 229910052760 oxygen Inorganic materials 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 32
- 230000005587 bubbling Effects 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 24
- 239000007888 film coating Substances 0.000 claims description 18
- 238000009501 film coating Methods 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010309 melting process Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 65
- 239000010410 layer Substances 0.000 description 34
- 238000002834 transmittance Methods 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000000265 homogenisation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 5
- 230000011218 segmentation Effects 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000005385 borate glass Substances 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Classifications
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of optical materials, in particular to ultraviolet-resistant high-refraction optical glass and a preparation method thereof, wherein the raw materials comprise 25.35-32.58% of boric acid, 36.45-41.42% of lanthanum oxide, 4.05-5.15% of zirconium oxide, 1.45-1.68% of quartz sand, 9.45-12.56% of niobium oxide and 0.02-0.03% of antimony oxide by mass percent, and the optical glass slice is prepared by controlling the raw materials to be sequentially subjected to melting, clarifying, homogenizing, forming and annealing treatment. According to the anti-ultraviolet high-refraction optical glass and the preparation method thereof, the specific raw material proportion is adopted, so that the production cost of the optical glass is greatly reduced, the refractive index of the optical glass is effectively increased, the melting temperature of the optical glass is reduced, the content of hydroxyl in raw material liquid is reduced under a specific process, the refractive index and the physical property of the optical glass are effectively ensured and improved, and the prepared optical glass finished product has high interval refractive index and excellent anti-ultraviolet function.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to ultraviolet-resistant high-refraction optical glass and a preparation method thereof.
Background
The optical glass can change the propagation direction of light and change the relative spectral distribution of ultraviolet, visible or infrared light. Optical glass in the narrow sense means colorless optical glass; the optical glass in a broad sense also includes colored optical glass, laser glass, quartz optical glass, radiation-resistant glass, ultraviolet infrared optical glass, fiber optical glass, acousto-optic glass, magneto-optic glass and photochromic glass. The optical glass can be used for manufacturing lenses, prisms, reflectors, windows and the like in optical instruments. Components made of optical glass are critical elements in optical instruments.
On the other hand, excessive ultraviolet rays are harmful to human bodies, and when the ultraviolet rays act on the human bodies for a long time, a series of changes can occur to human body functions, particularly, the damage can be caused to the skin, research and immune systems of the human bodies, the health state of the human bodies is reduced, such as skin relaxation and elasticity reduction, and skin cancer can be induced more seriously; in addition, ultraviolet rays accelerate the aging of the article, and the article loses the original luster.
In the existing optical glass technology, for example, an optical glass disclosed in chinese patent publication No. CN112624606A includes a glass layer and a protective layer; the protective layer is coated on the outer side of the glass layer; the protective layer is made of elastic solid material; the optical glass is composed of the following raw materials: 8-10 parts of silicon dioxide, 24-25 parts of lanthanum trioxide, 16-20 parts of boron trioxide, 8-12 parts of nano titanium dioxide, 5-8 parts of aluminum oxide, 5-8 parts of lithium oxide, 1-1.6 parts of barium oxide, 2-4 parts of fish oil, 8-6 parts of microcrystalline paraffin, 8-10 parts of low molecular weight polyethylene resin, 12-16 parts of polyamide-6, 2-3 parts of calcium oxide and 3-5 parts of heat-conducting carbon fibers; the optical glass is prepared into double layers, and the protective layer is added on the outer layer, so that the shock resistance and the corrosion resistance of the optical glass can be effectively enhanced, and meanwhile, the cleaning process before secondary molding or precision molding is omitted, so that the process of preparing the optical part by precision molding of the optical glass is more convenient. However, the refractive index of the optical glass is low, and effective interception of ultraviolet rays cannot be performed.
Therefore, the invention provides the anti-ultraviolet high-refraction optical glass and the preparation method thereof, wherein the refractive index of the optical glass is effectively increased, so that the prepared optical glass finished product has high interval refractive index and excellent ultraviolet-proof function.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the anti-ultraviolet high-refraction optical glass and the preparation method thereof2O5The production cost of the optical glass is greatly reduced, the refractive index of the optical glass is effectively increased, the melting temperature of the optical glass is reduced, the content of hydroxyl in raw material liquid is reduced under a specific process, and the refractive index and the physical property of the optical glass are effectively ensured and improvedAnd (4) performance.
The purpose of the invention is realized by the following technical scheme:
a preparation method of anti-ultraviolet high-refraction optical glass comprises the following steps,
step S1, mixing 25.35-32.58% of boric acid, 36.45-41.42% of lanthanum oxide, 4.05-5.15% of zirconium oxide, 1.45-1.68% of quartz sand, 9.45-12.56% of niobium oxide, 0.02-0.03% of antimony oxide and the balance of zinc oxide according to mass percentage, and putting the mixture into a tank furnace;
step S2, controlling the raw materials to be melted in a tank furnace, wherein the working temperature of the tank furnace is 1300 +/-20 ℃, the melting time is 5 hours, and in the melting process, introducing dry nitrogen above the raw materials in the tank furnace for atmosphere protection, and introducing dry oxygen from the bottom of the tank furnace for bubbling;
step S3, clarifying the melted raw material for 4h, introducing dry nitrogen for atmosphere protection in the clarifying process, controlling the ambient temperature to 1400 +/-20 ℃, and simultaneously introducing dry oxygen from the bottom of the raw material for bubbling;
step S4, introducing the materials into a stirring tank, stirring and homogenizing for 1h, introducing dry nitrogen above the raw materials for atmosphere protection during the stirring and homogenizing treatment, wherein the ambient temperature of the stirring tank is 1250 +/-20 ℃, and introducing dry oxygen from the bottom of the stirring tank for bubbling;
s5, molding the material, and controlling the molding working temperature to be 1000-1050 ℃; after finishing shaping, immediately entering a traction furnace for annealing treatment, and controlling the annealing rate to be 25 ℃/h; after annealing is finished, uniformly dividing the material, manufacturing an optical glass substrate, then performing film coating treatment on the optical glass substrate by using monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant through a film coating machine, and obtaining the ultraviolet-resistant high-refraction optical glass.
In the selection of raw materials, boric acid is selected as a main component forming a glass skeleton, and the boric acid is used as a reducing agentA low glass melt viscosity co-solvent; boric acid as a glass skeleton, boron-oxygen trigonal [ BO3]3-And boron-oxygen tetrahedron [ BO4]4-Boron may be in the form of a trigonal [ BO ] under different conditions as a structural element3]3-Or boron-oxygen tetrahedron [ BO4]4-In the presence of B, it is difficult to form boron-oxygen tetrahedron under high-temperature melting conditions, but B is present only in the form of trihedron under certain conditions at low temperature3+The glass has the tendency of capturing free oxygen to form tetrahedron, so that the structure is compact, the low-temperature viscosity of the glass is improved, but the glass has the characteristics of reducing the viscosity of the glass at high temperature and improving the viscosity of the glass at low temperature and is also a main component for reducing the refractive index of the glass, so that the content range of the glass is determined to be smaller; when the boric acid content in the raw materials is low, the boric acid cannot play a role in assisting dissolution, and the chemical stability of the glass can be reduced; when the content of the boric acid is higher, the refractive index of the glass is reduced, the phase separation tendency of the glass is increased, and the boric acid with the mass percent of 25.35-32.58% is preferably adopted in combination with the characteristics of the rest raw materials.
Lanthanum oxide is lanthanide rare earth oxide, can improve the refractive index of the glass, when the content of lanthanum oxide in the glass is low, the glass can not reach the required high refractive index, when the content is high, the devitrification resistance of the glass is poor, the high-temperature viscosity is low, the glass is not beneficial to glass forming, and by combining the characteristics of the rest raw materials, the lanthanum oxide with the mass percentage of 36.45-41.42% is preferably adopted.
The zirconia has high refractive index and low dispersion property, and can improve the chemical stability of the glass and improve the refractive index and transmittance of the glass when being introduced into the glass; when a large amount of rare earth ions exist in the glass, a certain amount of zirconia is introduced, so that the crystallization tendency of the glass can be reduced; however, when the amount of zirconia is too high, the crystallization upper limit temperature of the glass is increased, the crystallization speed is increased, and the crystallization resistance of the glass is deteriorated; in addition, Zr has small ionic radius, high charge and large ionic field strength, and when excessive Zr is introduced into the glass, anions can be accumulated, so that the glass tends to generate phase separation; when the content of zirconia is too low, the effect cannot be achieved, and when the content of zirconia is too high, the melting temperature of glass and the crystallization tendency of glass are increased, so that zirconia with the mass percent of 4.05-5.15% is preferably adopted in combination with the characteristics of the rest raw materials.
The quartz sand is a glass forming body oxide and is an effective component for improving the viscosity, the anti-crystallization performance and the chemical stability of the glass; if the content of the quartz sand is too small, the quartz sand cannot play a role, and if the content is too high, the meltability of the glass is deteriorated, and the crystallization upper limit temperature is increased; in addition, through research and experiment, the B/Si ratio in the glass has a crucial influence on the performance of the glass, the structure of the borate glass determines that the borate glass has poor chemical stability, small high-temperature viscosity and easy devitrification, and in order to improve the properties of the borate glass, part of quartz sand is usually used for replacing B2O3The chemical stability of the glass is improved, the devitrification tendency is reduced, and the forming range of the glass is enlarged; the rare earth ions have high electrovalence, high field strength and weak ability of giving free oxygen, so if the content of boric acid in the raw materials is high, more boron-oxygen trigonal [ BO ] is generated in the glass3]3-When the boric acid content is reduced, quartz sand is introduced into the glass, and there is sufficient free oxygen in the glass, boron oxygen trigonal [ BO ]3]3-Conversion to boron-oxygen tetrahedron [ BO4]5-，[BO4]5-Between them is silicon-oxygen tetrahedron [ SiO ]4]4-Separating, and balancing three structural groups to strengthen the structural network and inhibit the generation of boron crystal compounds; the B/Si ratio has obvious influence on the anti-devitrification performance of the glass and also has obvious influence on the refractive index of the glass, and when the B/Si ratio is reduced, the refractive index of the glass is increased, so that quartz sand with the mass ratio of 1.45-1.68% is preferably adopted in combination with the characteristics of other raw materials.
Niobium oxide and zinc oxide can increase the refractive index of the optical glass and reduce the melting temperature of the optical glass, and the niobium oxide usually takes six-coordination octahedron as a stable structure in the glass and can enter a glass network to play a role of a glass forming body. When the glass is excessively added, the free oxygen in the glass is insufficient, and the glass plays a role of a network intermediate and reduces the generation of the glassThe forming ability; the zinc oxide is added into the rare earth optical glass, so that the chemical stability of the glass is improved, the liquidus temperature is reduced, the high-temperature viscosity is reduced, and the anti-crystallization performance of the glass is improved; the zinc is in the glass [ ZnO ]6]6-And [ ZnO ]4]2-Two coordination states, the right amount of zinc is [ ZnO ] in the glass4]2-In the coordination state, the four-coordination Zn has the function of connecting a glass network, so that the crystallization resistance of the glass is improved; however, when Zn is excessive in the glass, it causes hexacoordination [ ZnO ] in the glass6]6-The content is increased, so that the devitrification resistance of the glass is deteriorated; niobium oxide and zinc oxide with the sum of the mass percent of 25.46-28.13% are preferably adopted, so that the refractive index of the optical glass can be increased, the melting temperature of the optical glass can be reduced, and the expensive raw material Ta adopted in the traditional method can be effectively replaced2O5And the production cost of the optical glass is greatly reduced.
Further, in step S2, dry nitrogen is introduced into the tank furnace from top to bottom at a rate of 0.6 to 0.8L/min, and simultaneously introduced from left to right at a rate of 1.2 to 1.6L/min, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere. In the melting, clarifying and homogenizing processes of raw materials, under the protection treatment of a common nitrogen atmosphere, although most of water in the raw materials can be evaporated at high temperature, a small part of water still remains in the raw materials in the form of hydroxyl, and the hydroxyl can loosen the structure of the finished optical glass to cause the physicochemical property and the refractive index to be poor.
Further, in step S2, dry oxygen is introduced from the bottom of the raw material at a rate of 0.1 to 0.2L/min for bubbling for the first 5 to 15min, then dry oxygen is introduced from the bottom of the raw material at a rate of 0.4 to 0.6L/min for bubbling for 2h, and then dry oxygen is introduced from the bottom of the raw material at a rate of 0.15 to 0.25L/min until the melting process is completed.
Further, in step S3, dry nitrogen gas is introduced from front to back to perform atmosphere protection.
Further, in step S3, the dry nitrogen is introduced at a rate of 0.8-1.2L/min, and the ratio of the dry nitrogen to the dry oxygen is 10: 2-6.
Further, in step S4, the stirring rate is controlled to be 20. + -.1 Hz.
Further, in step S4, in the stirring and homogenizing process, a bottom layer stirring paddle and a top layer stirring paddle are respectively disposed in the stirring tank, the top layer stirring paddle is located above the bottom layer stirring paddle, the working surface of the top layer stirring paddle is parallel to the horizontal plane, and the included angle between the working surface of the bottom layer stirring paddle and the horizontal plane is 15 ° to 30 °. Through specific stirring paddle and stirring mode, the stirring homogenization of the glass liquid is more efficient and thorough, the stripes of the glass optical glass are effectively controlled, and the market competitiveness of the product is improved.
Further, in step S4, the dry nitrogen is introduced at a rate of 0.6-1.2L/min, and the ratio of the dry nitrogen to the dry oxygen is 10: 2-6.
Further, in step S5, the annealing is performed in a pulling furnace, in which the temperature gradually decreases along the material traveling direction, the leading end temperature is 680 ℃, and the trailing end temperature is 230 ℃.
Further, in step S5, when the annealing treatment is performed, the temperature in the traction furnace is controlled to be divided into 12 temperature zones along the material traveling direction, and the temperatures of the 12 temperature zones are 680 ℃, 670 ℃, 660 ℃, 630 ℃, 600 ℃, 560 ℃, 510 ℃, 450 ℃, 390 ℃, 330 ℃, 280 ℃ and 230 ℃ respectively. After the shaping is finished, the glass enters a traction furnace immediately for annealing treatment, and the annealing process formed by a specific temperature zone is utilized to effectively eliminate the stress of the formed optical glass and ensure the production quality of the optical glass.
Further, in step S1, the sum of the mass percentages of the niobium oxide and the zinc oxide is 25.46-28.13%.
Further, after the material uniform segmentation treatment is finished, the uniformly segmented optical glass is made into an optical glass substrate, and then the optical glass substrate is subjected to film coating treatment by a film coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant. Preferably, in the coating treatment process, the flow rate of the carrier gas is controlled to be 18L/min, the temperature of the evaporator is 155 ℃, the speed of the substrate is 3mm/s, and the temperature of the substrate is 580 ℃.
The anti-ultraviolet high-refraction optical glass is prepared by the preparation method.
The invention has the beneficial effects that: the invention relates to an anti-ultraviolet high-refraction optical glass and a preparation method thereof2O5The production cost of the optical glass is greatly reduced, the refractive index of the optical glass is effectively increased, the melting temperature of the optical glass is reduced, the content of hydroxyl in raw material liquid is reduced under a specific process, the refractive index and the physical property of the optical glass are effectively ensured and improved, and the prepared optical glass finished product has high interval refractive index and excellent ultraviolet-proof function.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to examples, but the scope of the present invention is not limited to the following.
Example 1
An ultraviolet-resistant high-refraction optical glass is prepared by the method comprising the following steps:
step S1, mixing 29.54% of boric acid, 38.33% of lanthanum oxide, 4.65% of zirconium oxide, 1.54% of quartz sand, 10.36% of niobium oxide, 0.025% of antimony oxide and the balance of zinc oxide, and putting the mixture into a tank furnace, wherein the sum of the mass percentages of the niobium oxide and the zinc oxide is 25.46-28.13%;
step S2, controlling the raw materials to be melted in a tank furnace, wherein the working temperature of the tank furnace is 1300 +/-20 ℃, the melting time is 5 hours, and in the melting process, introducing dry nitrogen gas from top to bottom at a rate of 0.6-0.8L/min, and simultaneously introducing dry nitrogen gas from left to right at a rate of 1.2-1.6L/min, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere; in addition, 5min before the melting treatment, introducing dry oxygen from the bottom of the raw material at a rate of 0.1-0.2L/min for bubbling, then introducing dry oxygen from the bottom of the raw material at a rate of 0.4-0.6L/min for bubbling within 2h, and then introducing dry oxygen from the bottom of the raw material at a rate of 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw material for 4h, introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introduction amount of the dry nitrogen is 0.8-1.2L/min, and introducing dry oxygen from the bottom of the raw material for bubbling, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 5;
step S4, introducing the materials into a stirring tank, stirring and homogenizing for 1h, controlling the stirring speed to be 20 +/-1 Hz, introducing dry nitrogen above the raw materials for atmosphere protection in the stirring and homogenizing process, wherein the ambient temperature of the stirring tank is 1250 +/-20 ℃, introducing dry oxygen from the bottom of the stirring tank for bubbling, the introduction amount of the dry nitrogen is 0.6-1.2L/min, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 5; in the stirring homogenization treatment process, a bottom layer stirring paddle and a top layer stirring paddle are respectively arranged in a stirring tank, the top layer stirring paddle is positioned above the bottom layer stirring paddle, the working surface of the top layer stirring paddle is parallel to the horizontal plane, the included angle between the working surface of the bottom layer stirring paddle and the horizontal plane is 20 degrees, the stirring homogenization of the glass liquid is more efficient and thorough through a specific stirring paddle and a stirring mode, the stripes of the glass optical glass are effectively controlled, and the market competitiveness of the product is improved;
in addition, in the melting, clarifying and homogenizing processes of the raw materials, under the protection treatment of a common nitrogen atmosphere, although most of water in the raw materials can be evaporated at high temperature, a small part of water still remains in the raw materials in the form of hydroxyl, and the hydroxyl can loosen the structure of the finished optical glass to cause the physicochemical property and the refractive index to be poor;
s5, molding the material, and controlling the molding working temperature to be 1000-1050 ℃; after finishing shaping, immediately carrying out annealing treatment, wherein the annealing is finished in a traction furnace, the temperature in the traction furnace is gradually reduced along the material advancing direction, the temperature of the front end is 680 ℃, the temperature of the tail end is 230 ℃, the annealing speed is controlled to be 25 ℃/h, specifically, the traction furnace is divided into 12 temperature sections along the material advancing direction, and the temperatures of the 12 temperature sections are 680 ℃, 670 ℃, 660 ℃, 630 ℃, 600 ℃, 560 ℃, 510 ℃, 450 ℃, 390 ℃, 330 ℃, 280 ℃ and 230 ℃ respectively; after the annealing is finished, uniformly dividing the material; after the material uniform segmentation treatment is finished, the uniformly segmented optical glass is made into an optical glass substrate, then, the optical glass substrate is subjected to film coating treatment by a film coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant, and in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is 155 ℃, the substrate speed is 3mm/s, and the substrate temperature is 580 ℃, so that an optical glass finished product is prepared.
The performance of the prepared optical glass finished product is detected to obtain the refractive index nd1.883, Abbe number vdIs 42.32, angle of refraction θd356.423 degrees, stress of 25nm/cm, visible light transmittance of 86.86 percent, square resistance of 9.6 omega/sq, ultraviolet light transmittance of less than or equal to 5 percent and near infrared light transmittance of less than or equal to 20 percent.
Example 2
An ultraviolet-resistant high-refraction optical glass is prepared by the method comprising the following steps:
step S1, mixing 25.35% boric acid, 41.42% lanthanum oxide, 5.05% zirconium oxide, 1.52% quartz sand, 9.45% niobium oxide, 0.02% antimony oxide and the balance zinc oxide into a tank furnace;
step S2, controlling the raw materials to be melted in a tank furnace, wherein the working temperature of the tank furnace is 1300 +/-20 ℃, the melting time is 5 hours, and in the melting process, introducing dry nitrogen gas from top to bottom at a rate of 0.6-0.8L/min, and simultaneously introducing dry nitrogen gas from left to right at a rate of 1.2-1.6L/min, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere; in addition, introducing dry oxygen from the bottom of the raw material for bubbling at a rate of 0.1-0.2L/min within 10min before the melting treatment, introducing dry oxygen from the bottom of the raw material for bubbling at a rate of 0.4-0.6L/min within 2h, and introducing dry oxygen from the bottom of the raw material for bubbling at a rate of 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw material for 4h, introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introduction amount of the dry nitrogen is 0.8-1.2L/min, and introducing dry oxygen from the bottom of the raw material for bubbling, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 2;
step S4, introducing the materials into a stirring tank, stirring and homogenizing for 1h, controlling the stirring speed to be 20 +/-1 Hz, introducing dry nitrogen above the raw materials for atmosphere protection in the stirring and homogenizing process, wherein the ambient temperature of the stirring tank is 1250 +/-20 ℃, introducing dry oxygen from the bottom of the stirring tank for bubbling, the introduction amount of the dry nitrogen is 0.6-1.2L/min, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 6; in the stirring homogenization treatment process, a bottom layer stirring paddle and a top layer stirring paddle are respectively arranged in a stirring tank, the top layer stirring paddle is positioned above the bottom layer stirring paddle, the working surface of the top layer stirring paddle is parallel to the horizontal plane, and the included angle between the working surface of the bottom layer stirring paddle and the horizontal plane is 25 degrees;
s5, molding the material, and controlling the molding working temperature to be 1000-1050 ℃; after finishing shaping, immediately carrying out annealing treatment, wherein the annealing is finished in a traction furnace, the temperature in the traction furnace is gradually reduced along the material advancing direction, the temperature of the front end is 680 ℃, the temperature of the tail end is 230 ℃, the annealing speed is controlled to be 25 ℃/h, specifically, the traction furnace is divided into 12 temperature sections along the material advancing direction, and the temperatures of the 12 temperature sections are 680 ℃, 670 ℃, 660 ℃, 630 ℃, 600 ℃, 560 ℃, 510 ℃, 450 ℃, 390 ℃, 330 ℃, 280 ℃ and 230 ℃ respectively; after the annealing is finished, uniformly dividing the material; after the material uniform segmentation treatment is finished, the uniformly segmented optical glass is made into an optical glass substrate, then, the optical glass substrate is subjected to film coating treatment by a film coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant, and in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is 155 ℃, the substrate speed is 3mm/s, and the substrate temperature is 580 ℃, so that an optical glass finished product is prepared.
The performance of the prepared optical glass finished product is detected to obtain the refractive index ndIs 1.901, Abbe number vd41.24, angle of refraction θd355.961 degrees, stress of 25nm/cm, visible light transmittance of 85.46 percent, square resistance of 9.9 omega/sq, ultraviolet light transmittance of less than or equal to 5 percent and near infrared light transmittance of less than or equal to 20 percent.
Example 3
An ultraviolet-resistant high-refraction optical glass is prepared by the method comprising the following steps:
step S1, mixing 32.58% of boric acid, 36.45% of lanthanum oxide, 5.15% of zirconium oxide, 1.45% of quartz sand, 10.91% of niobium oxide, 0.03% of antimony oxide and the balance of zinc oxide in percentage by mass, and then putting the mixture into a tank furnace;
step S2, controlling the raw materials to be melted in a tank furnace, wherein the working temperature of the tank furnace is 1300 +/-20 ℃, the melting time is 5 hours, and in the melting process, introducing dry nitrogen gas from top to bottom at a rate of 0.6-0.8L/min, and simultaneously introducing dry nitrogen gas from left to right at a rate of 1.2-1.6L/min, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere; in addition, introducing dry oxygen from the bottom of the raw material for bubbling at a rate of 0.1-0.2L/min 15min before the melting treatment, introducing dry oxygen from the bottom of the raw material for bubbling at a rate of 0.4-0.6L/min within 2h, and introducing dry oxygen from the bottom of the raw material for bubbling at a rate of 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw material for 4h, introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introduction amount of the dry nitrogen is 0.8-1.2L/min, and introducing dry oxygen from the bottom of the raw material for bubbling, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 6;
step S4, introducing the materials into a stirring tank, stirring and homogenizing for 1h, controlling the stirring speed to be 20 +/-1 Hz, introducing dry nitrogen above the raw materials for atmosphere protection in the stirring and homogenizing process, wherein the ambient temperature of the stirring tank is 1250 +/-20 ℃, introducing dry oxygen from the bottom of the stirring tank for bubbling, the introduction amount of the dry nitrogen is 0.6-1.2L/min, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 2; in the stirring homogenization treatment process, a bottom layer stirring paddle and a top layer stirring paddle are respectively arranged in a stirring tank, the top layer stirring paddle is positioned above the bottom layer stirring paddle, the working surface of the top layer stirring paddle is parallel to the horizontal plane, and the included angle between the working surface of the bottom layer stirring paddle and the horizontal plane is 15 degrees;
s5, molding the material, and controlling the molding working temperature to be 1000-1050 ℃; after finishing shaping, immediately carrying out annealing treatment, wherein the annealing is finished in a traction furnace, the temperature in the traction furnace is gradually reduced along the material advancing direction, the temperature of the front end is 680 ℃, the temperature of the tail end is 230 ℃, the annealing speed is controlled to be 25 ℃/h, specifically, the traction furnace is divided into 12 temperature sections along the material advancing direction, and the temperatures of the 12 temperature sections are 680 ℃, 670 ℃, 660 ℃, 630 ℃, 600 ℃, 560 ℃, 510 ℃, 450 ℃, 390 ℃, 330 ℃, 280 ℃ and 230 ℃ respectively; after the annealing is finished, uniformly dividing the material; after the material uniform segmentation treatment is finished, the uniformly segmented optical glass is made into an optical glass substrate, then, the optical glass substrate is subjected to film coating treatment by a film coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant, and in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is 155 ℃, the substrate speed is 3mm/s, and the substrate temperature is 580 ℃, so that an optical glass finished product is prepared.
The performance of the prepared optical glass finished product is detected to obtain the refractive index ndIs 1.894, Abbe number vd42.04, angle of refraction θd356.384 degrees, stress of 25nm/cm, visible light transmittance of 86.46 percent, square resistance of 9.2 omega/sq, ultraviolet light transmittance of less than or equal to 5 percent and near infrared light transmittance of less than or equal to 20 percent.
Example 4
An ultraviolet-resistant high-refraction optical glass is prepared by the method comprising the following steps:
step S1, mixing the raw materials, by mass, 29.58% of boric acid, 38.71% of lanthanum oxide, 4.88% of zirconium oxide, 1.68% of quartz sand, 12.56% of niobium oxide, 0.02% of antimony oxide and the balance of zinc oxide, and then putting the mixture into a tank furnace;
step S2, controlling the raw materials to be melted in a tank furnace, wherein the working temperature of the tank furnace is 1300 +/-20 ℃, the melting time is 5 hours, and in the melting process, introducing dry nitrogen gas from top to bottom at a rate of 0.6-0.8L/min, and simultaneously introducing dry nitrogen gas from left to right at a rate of 1.2-1.6L/min, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere; in addition, 5-15 min before the melting treatment, introducing dry oxygen from the bottom of the raw material at a rate of 0.1-0.2L/min for bubbling, then introducing dry oxygen from the bottom of the raw material at a rate of 0.4-0.6L/min for bubbling within 2h, and then introducing dry oxygen from the bottom of the raw material at a rate of 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw material for 4h, introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introduction amount of the dry nitrogen is 0.8-1.2L/min, and introducing dry oxygen from the bottom of the raw material for bubbling, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 5;
step S4, introducing the materials into a stirring tank, stirring and homogenizing for 1h, controlling the stirring speed to be 20 +/-1 Hz, introducing dry nitrogen above the raw materials for atmosphere protection in the stirring and homogenizing process, wherein the ambient temperature of the stirring tank is 1250 +/-20 ℃, introducing dry oxygen from the bottom of the stirring tank for bubbling, the introduction amount of the dry nitrogen is 0.6-1.2L/min, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 4; in the stirring homogenization treatment process, a bottom layer stirring paddle and a top layer stirring paddle are respectively arranged in a stirring tank, the top layer stirring paddle is positioned above the bottom layer stirring paddle, the working surface of the top layer stirring paddle is parallel to the horizontal plane, and the included angle between the working surface of the bottom layer stirring paddle and the horizontal plane is 30 degrees;
s5, molding the material, and controlling the molding working temperature to be 1000-1050 ℃; after finishing shaping, immediately carrying out annealing treatment, wherein the annealing is finished in a traction furnace, the temperature in the traction furnace is gradually reduced along the material advancing direction, the temperature of the front end is 680 ℃, the temperature of the tail end is 230 ℃, the annealing speed is controlled to be 25 ℃/h, specifically, the traction furnace is divided into 12 temperature sections along the material advancing direction, and the temperatures of the 12 temperature sections are 680 ℃, 670 ℃, 660 ℃, 630 ℃, 600 ℃, 560 ℃, 510 ℃, 450 ℃, 390 ℃, 330 ℃, 280 ℃ and 230 ℃ respectively; after the annealing is finished, uniformly dividing the material; after the material uniform segmentation treatment is finished, the uniformly segmented optical glass is made into an optical glass substrate, then, the optical glass substrate is subjected to film coating treatment by a film coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant, and in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is 155 ℃, the substrate speed is 3mm/s, and the substrate temperature is 580 ℃, so that an optical glass finished product is prepared.
The performance of the prepared optical glass finished product is detected to obtain the refractive index ndIs 1.895, Abbe number vdIs 40.96 and angle of refraction thetad356.134 degrees, stress of 25nm/cm, visible light transmittance of 86.22 percent, square resistance of 9.4 omega/sq, ultraviolet light transmittance of less than or equal to 5 percent and near infrared light transmittance of less than or equal to 20 percent.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of anti-ultraviolet high-refraction optical glass is characterized by comprising the following steps,
step S1, mixing 25.35-32.58% of boric acid, 36.45-41.42% of lanthanum oxide, 4.05-5.15% of zirconium oxide, 1.45-1.68% of quartz sand, 9.45-12.56% of niobium oxide, 0.02-0.03% of antimony oxide and the balance of zinc oxide according to mass percentage, and putting the mixture into a tank furnace;
step S2, controlling the raw materials to be melted in a tank furnace, wherein the working temperature of the tank furnace is 1300 +/-20 ℃, the melting time is 5 hours, and in the melting process, introducing dry nitrogen above the raw materials in the tank furnace for atmosphere protection, and introducing dry oxygen from the bottom of the tank furnace for bubbling;
step S3, clarifying the melted raw material for 4h, introducing dry nitrogen for atmosphere protection in the clarifying process, controlling the ambient temperature to 1400 +/-20 ℃, and simultaneously introducing dry oxygen from the bottom of the raw material for bubbling;
step S4, introducing the materials into a stirring tank, stirring and homogenizing for 1h, introducing dry nitrogen above the raw materials for atmosphere protection during the stirring and homogenizing treatment, wherein the ambient temperature of the stirring tank is 1250 +/-20 ℃, and introducing dry oxygen from the bottom of the stirring tank for bubbling;
s5, molding the material, and controlling the molding working temperature to be 1000-1050 ℃; after finishing shaping, immediately entering a traction furnace for annealing treatment, and controlling the annealing rate to be 25 ℃/h; after annealing is finished, uniformly dividing the material, manufacturing an optical glass substrate, then performing film coating treatment on the optical glass substrate by using monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst and air as a carrier gas and an oxidant through a film coating machine, and obtaining the ultraviolet-resistant high-refraction optical glass.
2. The method for preparing an anti-ultraviolet high-refraction optical glass according to claim 1, wherein in step S2, dry nitrogen is introduced into the tank furnace from top to bottom at a rate of 0.6-0.8L/min, and dry nitrogen is introduced from left to right at a rate of 1.2-1.6L/min, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere.
3. The method for preparing an anti-ultraviolet high-refraction optical glass according to claim 1, wherein in step S2, dry oxygen is introduced from the bottom of the raw material at a rate of 0.1-0.2L/min for bubbling 5-15 min, then dry oxygen is introduced from the bottom of the raw material at a rate of 0.4-0.6L/min for bubbling 2h, and then dry oxygen is introduced from the bottom of the raw material at a rate of 0.15-0.25L/min until the melting process is finished.
4. The method for preparing an anti-ultraviolet high-refraction optical glass according to claim 1, wherein in step S3, dry nitrogen is introduced from front to back for atmosphere protection.
5. The method for preparing the ultraviolet-resistant high-refraction optical glass according to claim 4, wherein in the step S3, the introduction amount of the dry nitrogen is 0.8-1.2L/min, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 2-6.
6. The method for producing an ultraviolet-resistant high-refractive optical glass according to claim 1, wherein in step S4, the stirring rate is controlled to be 20 ± 1 Hz.
7. The method for preparing the ultraviolet-resistant high-refraction optical glass according to claim 1, wherein in the step S4, the introduction amount of the dry nitrogen is 0.6-1.2L/min, and the ratio of the introduction amount of the dry nitrogen to the introduction amount of the dry oxygen is 10: 2-6.
8. The method for manufacturing an anti-ultraviolet high-refraction optical glass according to claim 1, wherein in the step S5, when the annealing treatment is performed, the temperature in the drawing furnace is controlled to be divided into 12 temperature zones along the material traveling direction, and the temperatures of the 12 temperature zones are 680 ℃, 670 ℃, 660 ℃, 630 ℃, 600 ℃, 560 ℃, 510 ℃, 450 ℃, 390 ℃, 330 ℃, 280 ℃ and 230 ℃ respectively.
9. The method for preparing an anti-UV high-refraction optical glass according to claim 1, wherein in step S1, the sum of the mass percentages of niobium oxide and zinc oxide is 25.46-28.13%.
10. An ultraviolet-resistant high-refraction optical glass, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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