CN114163123B - Ultraviolet-resistant high-refraction optical glass and preparation method thereof - Google Patents
Ultraviolet-resistant high-refraction optical glass and preparation method thereof Download PDFInfo
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- CN114163123B CN114163123B CN202111369166.7A CN202111369166A CN114163123B CN 114163123 B CN114163123 B CN 114163123B CN 202111369166 A CN202111369166 A CN 202111369166A CN 114163123 B CN114163123 B CN 114163123B
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- 239000005304 optical glass Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 31
- 238000000137 annealing Methods 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- 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 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 16
- 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 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- 239000006004 Quartz sand Substances 0.000 claims abstract description 13
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 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 101
- 238000003756 stirring Methods 0.000 claims description 92
- 229910052757 nitrogen Inorganic materials 0.000 claims description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- 230000005587 bubbling Effects 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 23
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 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
- 238000000465 moulding Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000007493 shaping process Methods 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
- 239000002243 precursor Substances 0.000 claims description 7
- 238000010309 melting process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 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 4
- 230000000704 physical effect Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 65
- 239000007888 film coating Substances 0.000 description 14
- 238000009501 film coating Methods 0.000 description 14
- 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 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000005385 borate glass Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 230000036314 physical performance Effects 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
- 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 compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 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
- 201000010251 cutis laxa Diseases 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration 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
- 230000005611 electricity Effects 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
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 238000005191 phase separation Methods 0.000 description 1
- 238000007747 plating Methods 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
- 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
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 optical glass slices are prepared by controlling the raw materials to be sequentially subjected to melting, clarifying, homogenizing, forming and annealing treatment. According to the ultraviolet-resistant 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 properties of the optical glass are effectively ensured and improved, and the prepared optical glass finished product has high interval refractive index and excellent ultraviolet-resistant 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 can change the glass of the relative spectral distribution of ultraviolet, visible or infrared light. The narrow definition of optical glass refers to colorless optical glass; the broad sense optical glass 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. The component made of optical glass is a critical element in optical instruments.
On the other hand, the excessive ultraviolet rays are harmful to human bodies, and when the ultraviolet rays act on the human bodies for a long time, the human body functions can change in a series, and especially the skin, research and immune system of the human bodies can be damaged, so that the health state of the human bodies is reduced, such as loose skin and reduced elasticity, and skin cancer can be possibly induced more seriously; in addition, ultraviolet rays can also accelerate the aging of the articles, so that the articles lose the original luster.
In the prior art of optical glass, for example, an optical glass disclosed in Chinese patent publication No. CN112624606A comprises 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 materials; the optical glass is composed of the following raw materials: 8-10 parts of silicon dioxide, 24-25 parts of lanthanum oxide, 16-20 parts of diboron 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 fiber; the optical glass is prepared into a double layer, 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 pressing or precise pressing is omitted, so that the precise pressing process of the optical glass is more convenient. However, the optical glass has a low refractive index and cannot intercept ultraviolet rays effectively.
Therefore, the invention provides the ultraviolet-resistant high-refraction optical glass which can effectively increase the refractive index of the optical glass, so that the prepared optical glass finished product has high refractive index at intervals and excellent ultraviolet-resistant function, and the preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the ultraviolet-resistant high-refraction optical glass and the preparation method thereof, and the niobium oxide and the zinc oxide are used for replacing the expensive raw material Ta adopted in the traditional method by adopting specific raw material proportions 2 O 5 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, and the content of hydroxyl groups in the raw material liquid is reduced under a specific process, so that the refractive index and the physical performance of the optical glass are effectively ensured and improved.
The aim of the invention is realized by the following technical scheme:
a method for preparing ultraviolet resistant high refractive optical glass comprises the following steps,
step S1, mixing raw materials of 25.35 to 32.58 mass percent of boric acid, 36.45 to 41.42 mass percent of lanthanum oxide, 4.05 to 5.15 mass percent of zirconium oxide, 1.45 to 1.68 mass percent of quartz sand, 9.45 to 12.56 mass percent of niobium oxide, 0.02 to 0.03 mass percent 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 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 materials for 4 hours, introducing dry nitrogen in the clarifying process for atmosphere protection, controlling the ambient atmosphere temperature to be 1400+/-20 ℃, and simultaneously introducing dry oxygen from the bottom of the raw materials for bubbling;
step S4, introducing the materials into a stirring tank for stirring and homogenizing treatment, wherein the stirring treatment time is 1h, and in the stirring and homogenizing treatment process, introducing dry nitrogen above the raw materials for atmosphere protection, and introducing dry oxygen from the bottom of the stirring tank for bubbling, wherein the ambient atmosphere temperature of the stirring tank is 1250+/-20 ℃;
s5, carrying out molding treatment on the materials, and controlling the molding working temperature to be 1000-1050 ℃; immediately entering a traction furnace for annealing treatment after shaping, and controlling the annealing rate to-25 ℃/h; after annealing is finished, uniformly dividing the materials, preparing an optical glass substrate, and then coating the optical glass substrate by a coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst, air as a carrier gas and an oxidizing agent to obtain the ultraviolet-resistant high-refraction optical glass.
In the raw material selection, boric acid is selected as a main component forming a glass skeleton, and boric acid is used as a cosolvent for reducing glass melting viscosity; boric acid is used as a glass skeleton, and a boron-oxygen triangle [ BO ] 3 ] 3- And boron oxygen tetrahedra [ BO ] 4 ] 4- For structural elements, boron may be present in the form of a triangle [ BO ] 3 ] 3- Or boron oxygen tetrahedra [ BO ] 4 ] 4- In general, boron oxide tetrahedra are difficult to form under high temperature melting conditions, but only exist in a trihedral form, but B under certain conditions at low temperature 3+ The glass has the characteristics of reducing the glass viscosity at high temperature and improving the glass viscosity 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 material is lowThe glass cannot play a role in assisting dissolution, and meanwhile, the chemical stability of the glass is reduced; when the boric acid content is high, 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 of the invention.
The 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 glass has poor crystallization resistance and low high-temperature viscosity, is unfavorable for glass forming, and the lanthanum oxide with the mass percent of 36.45-41.42% is preferably adopted in combination with the characteristics of the rest raw materials of the invention.
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 the 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 introduced is too high, the upper limit temperature of crystallization of the glass is raised, the crystallization speed is increased, and the crystallization resistance of the glass is deteriorated; in addition, zr has small ionic radius, high charge and strong ionic field, and when excessive amount is introduced into glass, it can cause anion accumulation and tends to phase-separate the glass; on the other hand, if the zirconia content is too low, the effect is not exhibited, and if the zirconia content is too high, the melting temperature of the glass and the crystallization tendency of the glass are increased, so that it is preferable to use 4.05 to 5.15 mass% of zirconia in combination with the other raw material characteristics of the present invention.
Quartz sand is a glass forming oxide, and is an effective component for improving the viscosity, crystallization resistance and chemical stability of glass; if the content of the quartz sand is too small, the effect of the quartz sand cannot be achieved, 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 critical effect on the performance of the glass, the structure of the borate glass determines that the borate glass has poor chemical stability, low high-temperature viscosity and easy devitrification, and in order to improve the property of the borate glass, part of quartz sand is generally used for replacing B 2 O 3 Improving the chemical stability of the glass, reducing the devitrification tendency and increasing the forming range of the glass; the rare earth ion has high electricity price, high field intensity and weak capability of giving free oxygen, so if the content of boric acid in the raw material is more, more boron-oxygen triangulars [ BO ] are caused in the glass 3 ] 3- When the boric acid content is reduced and quartz sand is introduced into the glass, and when there is sufficient free oxygen in the glass, the boron oxide triangle [ BO 3 ] 3- Conversion to boron oxygen tetrahedra [ BO 4 ] 5- ，[BO 4 ] 5- Between by silicon oxygen tetrahedron [ SiO ] 4 ] 4- The three structural groups are separated to form balance, so that a structural network is reinforced, and the generation of boron crystal compounds is inhibited; the B/Si ratio has a remarkable influence on the glass refractive index as well as on the crystallization resistance of the glass, and when the B/Si ratio is lowered, the refractive index of the glass is raised, so that quartz sand with a mass ratio of 1.45-1.68% is preferably used in combination with the other raw material characteristics of the invention.
Niobium oxide and zinc oxide can increase the refractive index of the optical glass and reduce the melting temperature of the optical glass, and niobium oxide usually takes a hexacoordinated octahedron as a stable structure in the glass and can enter a glass network to play a role of a glass generator. When excessive glass is added, the free oxygen in the glass is insufficient, so that the glass plays a role of a network intermediate and reduces the generation capacity of the glass; 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 crystallization resistance of the glass is improved; zinc has [ ZnO in glass 6 ] 6- And [ ZnO ] 4 ] 2- In the two coordination states, proper amount of zinc is [ ZnO 4 ] 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 in the glass is excessive, hexacoordinated [ ZnO ] in the glass is caused 6 ] 6- The content is increased, so that the crystallization resistance of the glass is deteriorated; preferably, the niobium oxide and the zinc oxide with the mass percent of 25.46-28.13 percent are 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 effect can be achievedReplacing the expensive raw material Ta adopted in the traditional method 2 O 5 The production cost of the optical glass is greatly reduced.
Further, in the step S2, dry nitrogen is introduced from the top to the bottom at a rate of 0.6-0.8L/min and at the same time, dry nitrogen is introduced from the left to the right at a rate of 1.2-1.6L/min above the raw materials in the tank furnace, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere. In the process of melting, clarifying and homogenizing raw materials, under the common nitrogen atmosphere protection treatment, most of water in the raw materials can evaporate along with high temperature, but a small part of water still remains in the raw materials in the form of hydroxyl groups, and the hydroxyl groups can loosen the structure of the finished optical glass, so that the physical and chemical properties and refractive index are poor.
Further, in the step S2, the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.1-0.2L/min for bubbling for 5-15 min, then the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.4-0.6L/min for bubbling within 2h, and then the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.15-0.25L/min until the melting treatment is finished.
Further, in step S3, dry nitrogen is introduced from front to back for atmosphere protection.
Further, in the step S3, the inlet amount of the dry nitrogen is 0.8-1.2L/min, and the ratio of the inlet amount of the dry nitrogen to the inlet amount of the dry oxygen is 10:2-6.
Further, in step S4, the stirring rate is controlled to 20.+ -.1 Hz.
Further, in step S4, in the stirring and homogenizing process, a bottom stirring paddle and a top stirring paddle are respectively disposed in the stirring pool, the top stirring paddle is located above the bottom stirring paddle, a working surface of the top stirring paddle is parallel to a horizontal plane, and an included angle between the working surface of the bottom stirring paddle and the horizontal plane is 15 ° to 30 °. Through specific stirring paddles and stirring modes, the glass liquid is stirred and homogenized more efficiently and thoroughly, the stripes of the glass optical glass are effectively controlled, and the market competitiveness of the product is improved.
Further, in the step S4, the inlet amount of the dry nitrogen is 0.6-1.2L/min, and the ratio of the inlet amount of the dry nitrogen to the inlet amount of the dry oxygen is 10:2-6.
Further, in step S5, the annealing is completed in the traction furnace, the temperature in the traction furnace gradually decreases along the material traveling direction, the front end temperature is 680 ℃, and the tail end temperature is 230 ℃.
Further, in step S5, during the annealing treatment, the interior of the traction furnace is controlled to be divided into 12 temperature sections along the material travelling direction, and the temperatures of the 12 temperature sections are 680 ℃,670 ℃,660 ℃,630 ℃,600 ℃,560 ℃,510 ℃,450 ℃,390 ℃,330 ℃,280 ℃ and 230 ℃ respectively. And after shaping, the optical glass enters a traction furnace immediately for annealing treatment, and the stress of the optical glass after shaping is effectively eliminated by utilizing an annealing process formed by a specific temperature section, so that the production quality of the optical glass is ensured.
Further, in the step S1, the sum of the mass percentages of the niobium oxide and the zinc oxide is 25.46 to 28.13%.
Further, after the material is uniformly segmented, the optical glass is manufactured into an optical glass substrate, then monobutyl tin trichloride is used as a precursor, trifluoroacetic acid is used as a doping agent, deionized water is used as a catalyst, air is used as carrier gas and an oxidizing agent, and the optical glass substrate is subjected to film coating treatment by a film coating machine. Preferably, during the film plating process, the flow rate of the carrier gas is controlled to be 18L/min, the temperature of the evaporator is 155 ℃, the substrate speed is 3mm/s, and the substrate temperature is 580 ℃.
The ultraviolet-resistant high-refraction optical glass is prepared by the preparation method.
The beneficial effects of the invention are as follows: according to the ultraviolet-resistant high-refraction optical glass and the preparation method thereof, the expensive raw material T adopted in the traditional method is replaced by the niobium oxide and the zinc oxide by adopting the specific raw material proportiona 2 O 5 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 groups in the raw material liquid is reduced under a specific process, the refractive index and the physical performance of the optical glass are further 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 scheme of the present invention is described in further detail below with reference to examples, but the scope of the present invention is not limited to the following.
Example 1
The ultraviolet-resistant high-refraction optical glass is prepared by a 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 according to mass percent, and then placing the mixture into a tank furnace, wherein the sum of the mass percent of niobium oxide and the mass percent of zinc oxide is 25.46-28.13%;
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 at the speed of 0.6-0.8L/min from top to bottom and simultaneously introducing dry nitrogen at the speed of 1.2-1.6L/min from left to right above the raw materials in the tank furnace, 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 0.1-0.2L/min for bubbling, then introducing dry oxygen from the bottom of the raw material at 0.4-0.6L/min for bubbling within 2h, and then introducing dry oxygen from the bottom of the raw material at 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw materials for 4 hours, and introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introducing amount of the dry nitrogen is 0.8-1.2L/min, and simultaneously introducing dry oxygen from the bottom of the raw materials for bubbling, and the ratio of the introducing amount of the dry nitrogen to the introducing amount of the dry oxygen is 10:5;
s4, introducing the materials into a stirring tank for stirring and homogenizing treatment, wherein the stirring treatment time is 1h, the stirring speed is controlled to be 20+/-1 Hz, in the stirring and homogenizing treatment process, dry nitrogen is introduced above the raw materials for atmosphere protection, the ambient atmosphere temperature of the stirring tank is 1250+/-20 ℃, dry oxygen is introduced 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 stirring paddle and a top stirring paddle are respectively arranged in a stirring pool, the top stirring paddle is positioned above the bottom stirring paddle, the working face of the top stirring paddle is parallel to the horizontal plane, the included angle between the working face of the bottom stirring paddle and the horizontal plane is 20 degrees, and the glass liquid is stirred and homogenized more efficiently and thoroughly by a specific stirring paddle and stirring mode, so that the stripes of glass optical glass are effectively controlled, and the market competitiveness of products is improved;
in addition, under the common nitrogen atmosphere protection treatment in the melting, clarifying and homogenizing process of the raw materials, most of water in the raw materials can evaporate along with high temperature, but a small part of water still remains in the raw materials in the form of hydroxyl groups, and the hydroxyl groups can loosen the structure of the finished optical glass and cause the deterioration of physical and chemical properties and refractive indexes;
s5, carrying out molding treatment on the materials, and controlling the molding working temperature to be 1000-1050 ℃; immediately annealing after shaping is finished, finishing annealing in a traction furnace, wherein the temperature in the traction furnace is gradually reduced along the material travelling direction, the temperature at the front end is 680 ℃, the temperature at the tail end is 230 ℃, the annealing speed is-25 ℃/h, specifically, the temperature in the traction furnace is divided into 12 temperature sections along the material travelling 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 annealing is completed, uniformly dividing the materials; after the material is uniformly segmented, the uniformly segmented optical glass is manufactured into an optical glass substrate, then monobutyl tin trichloride is used as a precursor, trifluoroacetic acid is used as a doping agent, deionized water is used as a catalyst, air is used as carrier gas and an oxidizing agent, the optical glass substrate is subjected to film coating treatment by a film coating machine, in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is controlled to be 155 ℃, the substrate speed is controlled to be 3mm/s, and the substrate temperature is controlled to be 580 ℃ to obtain the optical glass finished product.
Detecting the performance of the optical glass finished product to obtain the refractive index n d 1.883 Abbe number v d Is 42.32, refraction angle theta d 356.423 DEG, stress of 25nm/cm, visible light transmittance of 86.86%, square resistance of 9.6 Ω/sq, ultraviolet light transmittance of 5% or less, and near infrared light transmittance of 20% or less.
Example 2
The ultraviolet-resistant high-refraction optical glass is prepared by a method comprising the following steps:
step S1, mixing raw materials including 25.35% of boric acid, 41.42% of lanthanum oxide, 5.05% of zirconium oxide, 1.52% of quartz sand, 9.45% of niobium oxide, 0.02% of antimony oxide and the balance of zinc oxide according to mass percent, and then putting the mixture into a tank furnace;
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 at the speed of 0.6-0.8L/min from top to bottom and simultaneously introducing dry nitrogen at the speed of 1.2-1.6L/min from left to right above the raw materials in the tank furnace, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere; in addition, the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.1-0.2L/min for bubbling 10min before the melting treatment, then the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.4-0.6L/min for bubbling within 2h, and then the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw materials for 4 hours, and introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introducing amount of the dry nitrogen is 0.8-1.2L/min, and simultaneously introducing dry oxygen from the bottom of the raw materials for bubbling, and the ratio of the introducing amount of the dry nitrogen to the introducing amount of the dry oxygen is 10:2;
s4, introducing the materials into a stirring tank for stirring and homogenizing treatment, wherein the stirring treatment time is 1h, the stirring speed is controlled to be 20+/-1 Hz, in the stirring and homogenizing treatment process, dry nitrogen is introduced above the raw materials for atmosphere protection, the ambient atmosphere temperature of the stirring tank is 1250+/-20 ℃, dry oxygen is introduced 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 stirring paddle and a top stirring paddle are respectively arranged in a stirring pool, the top stirring paddle is positioned above the bottom stirring paddle, the working face of the top stirring paddle is parallel to the horizontal plane, and the included angle between the working face of the bottom stirring paddle and the horizontal plane is 25 degrees;
s5, carrying out molding treatment on the materials, and controlling the molding working temperature to be 1000-1050 ℃; immediately annealing after shaping is finished, finishing annealing in a traction furnace, wherein the temperature in the traction furnace is gradually reduced along the material travelling direction, the temperature at the front end is 680 ℃, the temperature at the tail end is 230 ℃, the annealing speed is-25 ℃/h, specifically, the temperature in the traction furnace is divided into 12 temperature sections along the material travelling 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 annealing is completed, uniformly dividing the materials; after the material is uniformly segmented, the uniformly segmented optical glass is manufactured into an optical glass substrate, then monobutyl tin trichloride is used as a precursor, trifluoroacetic acid is used as a doping agent, deionized water is used as a catalyst, air is used as carrier gas and an oxidizing agent, the optical glass substrate is subjected to film coating treatment by a film coating machine, in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is controlled to be 155 ℃, the substrate speed is controlled to be 3mm/s, and the substrate temperature is controlled to be 580 ℃ to obtain the optical glass finished product.
Detecting the performance of the optical glass finished product to obtain the refractive index n d Is 1.901, abbe number v d 41.24, angle of refraction θ d 355.961 DEG, stress of 25nm/cm, visible light transmittance of 85.46%, square resistance of 9.9 ohm/sq, ultraviolet light transmittance of less than or equal to 5%, and near infrared light transmittance of less than or equal to 20%.
Example 3
The ultraviolet-resistant high-refraction optical glass is prepared by a method comprising the following steps:
step S1, mixing raw materials of 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 according to mass percent, and then putting the mixture into a tank furnace;
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 at the speed of 0.6-0.8L/min from top to bottom and simultaneously introducing dry nitrogen at the speed of 1.2-1.6L/min from left to right above the raw materials in the tank furnace, so that the raw materials in the tank furnace are melted under the protection of a regularly flowing nitrogen atmosphere; in addition, the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.1-0.2L/min for bubbling 15min before the melting treatment, then the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.4-0.6L/min for bubbling within 2h, and then the dry oxygen is introduced from the bottom of the raw material at the concentration of 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw materials for 4 hours, and introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introducing amount of the dry nitrogen is 0.8-1.2L/min, and simultaneously introducing dry oxygen from the bottom of the raw materials for bubbling, and the ratio of the introducing amount of the dry nitrogen to the introducing amount of the dry oxygen is 10:6;
s4, introducing the materials into a stirring tank for stirring and homogenizing treatment, wherein the stirring treatment time is 1h, the stirring speed is controlled to be 20+/-1 Hz, in the stirring and homogenizing treatment process, dry nitrogen is introduced above the raw materials for atmosphere protection, the ambient atmosphere temperature of the stirring tank is 1250+/-20 ℃, dry oxygen is introduced 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 stirring paddle and a top stirring paddle are respectively arranged in a stirring pool, the top stirring paddle is positioned above the bottom stirring paddle, the working face of the top stirring paddle is parallel to the horizontal plane, and the included angle between the working face of the bottom stirring paddle and the horizontal plane is 15 degrees;
s5, carrying out molding treatment on the materials, and controlling the molding working temperature to be 1000-1050 ℃; immediately annealing after shaping is finished, finishing annealing in a traction furnace, wherein the temperature in the traction furnace is gradually reduced along the material travelling direction, the temperature at the front end is 680 ℃, the temperature at the tail end is 230 ℃, the annealing speed is-25 ℃/h, specifically, the temperature in the traction furnace is divided into 12 temperature sections along the material travelling 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 annealing is completed, uniformly dividing the materials; after the material is uniformly segmented, the uniformly segmented optical glass is manufactured into an optical glass substrate, then monobutyl tin trichloride is used as a precursor, trifluoroacetic acid is used as a doping agent, deionized water is used as a catalyst, air is used as carrier gas and an oxidizing agent, the optical glass substrate is subjected to film coating treatment by a film coating machine, in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is controlled to be 155 ℃, the substrate speed is controlled to be 3mm/s, and the substrate temperature is controlled to be 580 ℃ to obtain the optical glass finished product.
Detecting the performance of the optical glass finished product to obtain the refractive index n d Is 1.894, abbe number v d 42.04, angle of refraction θ d 356.384 DEG, stress of 25nm/cm, visible light transmittance of 86.46%, square resistance of 9.2 ohm/sq, ultraviolet light transmittance of less than or equal to 5%, and near infrared light transmittance of less than or equal to 20%.
Example 4
The ultraviolet-resistant high-refraction optical glass is prepared by a method comprising the following steps:
step S1, mixing raw materials of 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 according to mass percent, and then putting the mixture into a tank furnace;
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 at the speed of 0.6-0.8L/min from top to bottom and simultaneously introducing dry nitrogen at the speed of 1.2-1.6L/min from left to right above the raw materials in the tank furnace, 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, bubbling by introducing dry oxygen from the bottom of the raw material at 0.1-0.2L/min, then bubbling by introducing dry oxygen from the bottom of the raw material at 0.4-0.6L/min within 2h, and then introducing dry oxygen from the bottom of the raw material at 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw materials for 4 hours, and introducing dry nitrogen from front to back for atmosphere protection in the clarifying process, wherein the introducing amount of the dry nitrogen is 0.8-1.2L/min, and simultaneously introducing dry oxygen from the bottom of the raw materials for bubbling, and the ratio of the introducing amount of the dry nitrogen to the introducing amount of the dry oxygen is 10:5;
s4, introducing the materials into a stirring tank for stirring and homogenizing treatment, wherein the stirring treatment time is 1h, the stirring speed is controlled to be 20+/-1 Hz, in the stirring and homogenizing treatment process, dry nitrogen is introduced above the raw materials for atmosphere protection, the ambient atmosphere temperature of the stirring tank is 1250+/-20 ℃, dry oxygen is introduced 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 stirring paddle and a top stirring paddle are respectively arranged in a stirring pool, the top stirring paddle is positioned above the bottom stirring paddle, the working face of the top stirring paddle is parallel to the horizontal plane, and the included angle between the working face of the bottom stirring paddle and the horizontal plane is 30 degrees;
s5, carrying out molding treatment on the materials, and controlling the molding working temperature to be 1000-1050 ℃; immediately annealing after shaping is finished, finishing annealing in a traction furnace, wherein the temperature in the traction furnace is gradually reduced along the material travelling direction, the temperature at the front end is 680 ℃, the temperature at the tail end is 230 ℃, the annealing speed is-25 ℃/h, specifically, the temperature in the traction furnace is divided into 12 temperature sections along the material travelling 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 annealing is completed, uniformly dividing the materials; after the material is uniformly segmented, the uniformly segmented optical glass is manufactured into an optical glass substrate, then monobutyl tin trichloride is used as a precursor, trifluoroacetic acid is used as a doping agent, deionized water is used as a catalyst, air is used as carrier gas and an oxidizing agent, the optical glass substrate is subjected to film coating treatment by a film coating machine, in the film coating treatment process, the carrier gas flow is controlled to be 18L/min, the evaporator temperature is controlled to be 155 ℃, the substrate speed is controlled to be 3mm/s, and the substrate temperature is controlled to be 580 ℃ to obtain the optical glass finished product.
Detecting the performance of the optical glass finished product to obtain the refractive index n d Is 1.895, abbe number v d 40.96, refraction angle θ d 356.134 DEG, stress of 25nm/cm, visible light transmittance of 86.22%, square resistance of 9.4 ohm/sq, ultraviolet light transmittance of less than or equal to 5%, and near infrared light transmittance of less than or equal to 20%.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (7)
1. A preparation method of ultraviolet-resistant high-refraction optical glass is characterized by comprising the following steps of,
step S1, mixing raw materials according to the mass percentage of 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, and then 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%;
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, in the melting process, introducing dry nitrogen above the raw materials in the tank furnace for atmosphere protection, introducing dry nitrogen from top to bottom at 0.6-0.8L/min, simultaneously introducing dry nitrogen from left to right at 1.2-1.6L/min, melting the raw materials in the tank furnace under the protection of a nitrogen atmosphere flowing regularly, introducing dry oxygen from the bottom of the tank furnace for bubbling, and introducing dry oxygen from the bottom of the raw materials for bubbling at the front 5-15 minutes, wherein the bubbling is performed after the bubbling is performed for 2 hours by introducing dry oxygen from the bottom of the raw materials at 0.1-0.2L/min, and then introducing dry oxygen from the bottom of the raw materials at 0.15-0.25L/min until the melting treatment is finished;
step S3, clarifying the melted raw materials for 4 hours, introducing dry nitrogen from front to back in the clarifying process for atmosphere protection, controlling the ambient atmosphere temperature to be 1400+/-20 ℃, and simultaneously introducing dry oxygen from the bottom of the raw materials for bubbling;
step S4, introducing materials into a stirring tank for stirring and homogenizing treatment, wherein the stirring treatment time is 1h, introducing dry nitrogen gas above the raw materials for atmosphere protection in the stirring and homogenizing treatment process, introducing dry oxygen gas from the bottom of the stirring tank for bubbling at the ambient atmosphere temperature of 1250+/-20 ℃, respectively arranging a bottom stirring paddle and a top stirring paddle in the stirring and homogenizing treatment process, wherein the top stirring paddle is positioned above the bottom stirring paddle, the working surface of the top stirring paddle is parallel to the horizontal plane, and the included angle between the working surface of the bottom stirring paddle and the horizontal plane is 15-30 degrees;
s5, carrying out molding treatment on the materials, and controlling the molding working temperature to be 1000-1050 ℃; immediately entering a traction furnace for annealing treatment after shaping, and controlling the annealing rate to-25 ℃/h; after annealing is finished, uniformly dividing the materials, preparing an optical glass substrate, and then coating the optical glass substrate by a coating machine by taking monobutyl tin trichloride as a precursor, trifluoroacetic acid as a doping agent, deionized water as a catalyst, air as a carrier gas and an oxidizing agent to obtain the ultraviolet-resistant high-refraction optical glass.
2. The method for preparing ultraviolet-resistant high-refraction optical glass according to claim 1, wherein in the step S3, the inlet amount of dry nitrogen is 0.8-1.2L/min, and the ratio of the inlet amount of dry nitrogen to the inlet amount of dry oxygen is 10:2-6.
3. The method for producing an ultraviolet-resistant high refractive optical glass according to claim 1 or 2, wherein in step S4, the stirring rate is controlled to 20±1Hz.
4. The method for preparing an ultraviolet resistant high refractive optical glass according to claim 1 or 2, wherein in the step S4, the inlet amount of dry nitrogen is 0.6-1.2L/min, and the ratio of the inlet amount of dry nitrogen to the inlet amount of dry oxygen is 10:2-6.
5. The method according to claim 1 or 2, wherein in step S5, the annealing treatment is performed by controlling the temperature in the pulling furnace to be divided into 12 temperature sections along the material traveling direction, wherein the temperatures of the 12 temperature sections are 680 ℃,670 ℃,660 ℃,630 ℃,600 ℃,560 ℃,510 ℃,450 ℃,390 ℃,330 ℃,280 ℃ and 230 ℃, respectively.
6. The method for preparing an ultraviolet-resistant high-refraction optical glass according to claim 1 or 2, wherein in the step S1, the sum of the mass percentages of the niobium oxide and the zinc oxide is 25.46-28.13%.
7. The anti-ultraviolet high-refraction optical glass is characterized by being prepared by the preparation method of any one of claims 1-6, wherein the refractive index of the anti-ultraviolet high-refraction optical glass is 1.883-1.901, and the Abbe number is 40.96-42.32.
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