CN111217524B - High-refractive-index mid-infrared optical glass and preparation method thereof - Google Patents
High-refractive-index mid-infrared optical glass and preparation method thereof Download PDFInfo
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- CN111217524B CN111217524B CN201811422171.8A CN201811422171A CN111217524B CN 111217524 B CN111217524 B CN 111217524B CN 201811422171 A CN201811422171 A CN 201811422171A CN 111217524 B CN111217524 B CN 111217524B
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- 239000005304 optical glass Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 24
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 24
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 238000010309 melting process Methods 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 230000010512 thermal transition Effects 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 238000010923 batch production Methods 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000013307 optical fiber Substances 0.000 abstract description 3
- 231100000701 toxic element Toxicity 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 6
- 238000005273 aeration Methods 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/253—Silica-free oxide glass compositions containing germanium
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 high-refractive-index intermediate infrared optical glass and a preparation method thereof, belonging to the technical field of optical glass. The high-refractive-index intermediate infrared optical glass comprises the following components in parts by mole: 35-50 parts of GeO225-30 parts of Ga2O312-20 parts of BaO and 15-20 parts of Bi2O33-10 parts of ZrO2And 2-5 parts of Ta2O5Grinding GeO2And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 800-1000 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the materials, heating to about 1300 ℃ again, adding ZrO2And Ta2O5Heating to about 1500 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 40-90 minutes; strong anti-crystallization capability, and difficult crystallization in the process of drawing the optical fiber; the infrared transmission range of the glass is 0.65-10 mu m, the transmittance is about 88%, and the refractive index is greater than 3.0; does not contain toxic elements such as lead, cadmium and the like to the environment and the human body; the glass has low price and is easy to realize batch production.
Description
Technical Field
The invention relates to high-refractive-index intermediate infrared optical glass and a preparation method thereof, belonging to the technical field of optical glass.
Background
Optical glasses are glasses that change the direction of light propagation 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.
Optical glass is the basis and important component of the photoelectric technology industry; with the sustainable and stable development of domestic economy, the optical glass manufacturing industry in China develops rapidly.
The raw materials for producing the optical glass are some oxides, hydroxides, nitrates and carbonates, and phosphates or fluorides are introduced according to the requirements of the formulation. In order to ensure the transparency of the glass, the content of colouring impurities, such as iron, chromium, copper, manganese, cobalt, nickel, etc., must be strictly controlled. The materials are required to be accurately weighed and uniformly mixed during the material preparation. The main production processes are smelting, forming, annealing and inspection.
Bi is a main component in many conventional optical glasses2O3Its pure product has alpha type, beta type and delta type. Alpha-type crystal is yellow monoclinic crystal, has relative density of 8.9, melting point of 825 deg.C, is soluble in acid, and is insoluble in water and alkali. The beta-form is bright yellow to orange, tetragonal system, relative density of 8.55, melting point of 860 ℃, acid-soluble and water-insoluble. Can be easily reduced into metal bismuth by hydrogen, hydrocarbon and the like. delta-Bi 2O3 is a special material having a cubic fluorite type structure in which 1/4 oxygen ion sites are vacant in the lattice, thereby having a very high oxygen ion conductivity. The main application objects of the bismuth oxide are electronic ceramic powder materials, electrolyte materials, photoelectric materials, high-temperature superconducting materials and catalysts. Bismuth oxide is used as an important additive in electronic ceramic powder materials, the purity of the bismuth oxide is generally required to be more than 99.15%, and the bismuth oxide is mainly applied to three types of zinc oxide piezoresistors, ceramic capacitors and ferrite magnetic materials; defects in refraction and infrared transmission even when TiO is formulated2And PbO, are not desirable in many applications where high refraction and infrared transmission are required.
Disclosure of Invention
The invention aims to provide the high-refractive-index mid-infrared optical glass with reasonable design and convenient operation and the preparation method thereof aiming at the defects and the defects of the prior art; the refractive index nd of the high-refractive-index intermediate infrared optical glass is between 3.1 and 3.68, and the Abbe number upsilond is between 20 and 22.
In order to achieve the purpose, the invention adopts the technical scheme that: the high-refractive-index intermediate infrared optical glass comprises the following components in parts by mole:
the preparation method of the high-refractive-index mid-infrared optical glass comprises the following steps:
1. selecting 35-50 parts of GeO225-30 parts of Ga2O312-20 parts of BaO and 15-20 parts of Bi2O33-10 parts of ZrO2And 2-5 parts of Ta2O5(ii) a Fully grinding the raw materials respectively for later use;
2. grinding GeO2And Ga2O3Mixing, mixing BaO and Bi2O3Mixing for later use;
3. the ground GeO obtained in the step 22And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 800-1000 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the materials, heating to about 1300 ℃ again, adding ZrO2And Ta2O5Heating to about 1500 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 40-90 minutes;
4. when the mixture is melted, standing for 30 minutes, cooling to 600-800 ℃, introducing high-purity oxygen and stirring for 40-60 minutes, and ensuring that the temperature is controlled to be about 700 ℃ during stirring;
5. stopping ventilation when stirring is finished, and clarifying and homogenizing at the temperature of 1000-1150 ℃ for about two hours;
6. after homogenization, the temperature is increased to about 1400 ℃ again, and high-speed stirring is carried out;
7. immediately cooling the stirred glass liquid to 800-1000 ℃, then pouring the glass liquid into a preheated mold for molding, and controlling the temperature of the preheated mold within 1200 ℃;
8. and (3) after the glass liquid in the mold is hardened, rapidly sending the glass liquid into a furnace which is heated to the temperature near the glass transition temperature in advance for annealing, and cooling to room temperature at the speed of 20-30 ℃/hour after heat preservation for 2-3 hours to obtain the high-refractive-index mid-infrared optical glass.
Preferably, the high-refractive-index intermediate infrared optical glass comprises the following components in parts by mole:
the high-refractive-index intermediate infrared optical glass has the infrared band transmission range of 0.65-10 mu m, the thermal transition temperature Tg range of 400-580 ℃, the high refractive index nd of 3.1-3.68, the thermal expansion coefficient of 19-23.8 ppm/DEG C and the Vickers hardness of 2.03-2.78 GPa.
After adopting the structure, the invention has the beneficial effects that: the high-refractive-index intermediate infrared optical glass and the preparation method thereof have strong crystallization resistance, and are not easy to crystallize in the process of drawing an optical fiber; the infrared transmission range of the glass is 0.65-10 mu m, the transmittance is about 88%, and the refractive index is greater than 3.0; does not contain toxic elements such as lead, cadmium and the like to the environment and the human body; the glass has low price, is easy to realize batch production, and is suitable for preparing infrared windows and infrared light path lenses.
Detailed Description
The first embodiment is as follows:
the high-refractive-index mid-infrared optical glass comprises the following components in parts by mole:
GeO235 parts of Ga2O326 parts of BaO 13 parts of Bi2O312.5 parts of ZrO25 parts of Nb2O58 parts of Ta2O52 parts of (1);
the preparation method of the high-refractive-index mid-infrared optical glass comprises the following steps:
1. 35 parts of GeO are selected226 parts of Ga2O313 parts of BaO and 12.5 parts of Bi2O35 parts of ZrO28 parts of Nb2O5And 2 parts of Ta2O5(ii) a Fully grinding the raw materials respectively for later use;
2. grinding GeO2And Ga2O3Mixing, mixing BaO and Bi2O3Mixing for later use;
3. the ground GeO obtained in the step 22And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 800-1000 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the mixed materials, heating to about 1300 ℃ again, adding ZrO2、Ta2O5And Nb2O5Heating to about 1500 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 45 minutes;
4. when the mixture is molten, standing for 25 minutes, cooling to 650 ℃, introducing high-purity oxygen and stirring for 45 minutes, and ensuring that the temperature is controlled to be about 700 ℃ during stirring;
5. stopping aeration when stirring is finished, and clarifying and homogenizing at 1000 ℃ for about two hours;
6. after homogenization, the temperature is increased to 1350 ℃ again, and high-speed stirring is carried out;
7. cooling the stirred glass liquid to 900 ℃ immediately, then pouring the glass liquid into a preheated mold for molding, and controlling the temperature of the preheated mold within 1200 ℃;
8. and (3) after the molten glass in the mold is hardened, quickly sending the molten glass into a furnace which is heated to the temperature near the glass transition temperature in advance for annealing, keeping the temperature for 2 hours, and then cooling to the room temperature at the speed of 25 ℃/hour to obtain the high-refractive-index intermediate infrared optical glass.
Example two:
the high-refractive-index mid-infrared optical glass comprises the following components in parts by mole:
GeO245 parts of Ga2O330 parts of BaO 17 parts of Bi2O320 parts of Ti, Nb2O55 parts of Ta2O57 parts of TiO23 parts of a mixture;
the preparation method of the high-refractive-index mid-infrared optical glass comprises the following steps:
1. selected GeO245 parts of Ga2O330 parts of BaO 17 parts of Bi2O320 parts of Ti, Nb2O55 parts of Ta2O57 parts of TiO23 parts of a mixture; fully grinding the raw materials respectively for later use;
2. grinding GeO2And Ga2O3Mixing, mixing BaO and Bi2O3Mixing for later use;
3. the ground GeO obtained in the step 22And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 950 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the mixed materials, heating to 1280 deg.C again, and adding Nb2O5、Ta2O5、TiO2Heating to 1460 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 70 minutes;
4. when the mixture is molten, standing for 30 minutes, cooling to 750 ℃, introducing high-purity oxygen and stirring for 50 minutes, and ensuring that the temperature is controlled to be about 700 ℃ during stirring;
5. stopping aeration when stirring is finished, and clarifying and homogenizing at 1100 ℃ for about two hours;
6. after homogenization, the temperature is increased to 1400 ℃ again, and high-speed stirring is carried out;
7. cooling the stirred molten glass to 950 ℃ immediately, then pouring the molten glass into a preheated mold for molding, and controlling the temperature of the preheated mold within 1200 ℃;
8. and (3) after the glass liquid in the mold is hardened, quickly sending the glass liquid into a furnace which is heated to the temperature near the glass transition temperature in advance for annealing, keeping the temperature for 2.5 hours, and then cooling to the room temperature at the speed of 20 ℃/hour to obtain the high-refractive-index intermediate infrared optical glass.
Example three:
the high-refractive-index mid-infrared optical glass comprises the following components in parts by mole:
GeO250 parts of Ga2O320 portions of BaO 20 portions and Bi2O325 parts of ZrO215 parts of Nb2O51 part of Ta2O53 parts of TiO22 parts of (1);
the preparation method of the high-refractive-index mid-infrared optical glass comprises the following steps:
1. selected GeO250 parts of Ga2O320 portions of BaO 20 portions and Bi2O325 parts of ZrO215 parts of Nb2O51 part of Ta2O53 parts of TiO22 parts of (1); fully grinding the raw materials respectively for later use;
2. grinding GeO2And Ga2O3Mixing, mixing BaO and Bi2O3Mixing for later use;
3. the ground GeO obtained in the step 22And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 800-1000 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the mixed materials, heating to about 1300 ℃ again, adding ZrO2And Nb2O5、Ta2O5Heating to about 1500 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 90 minutes;
4. when the mixture is molten, standing for 35 minutes, cooling to 800 ℃, introducing high-purity oxygen and stirring for 60 minutes, and ensuring that the temperature is controlled to be about 700 ℃ during stirring;
5. stopping aeration when stirring is finished, and clarifying and homogenizing at 1150 ℃ for about two hours;
6. after homogenization, the temperature is increased to 1450 ℃ again, and high-speed stirring is carried out;
7. cooling the stirred glass liquid to 1000 ℃ immediately, then pouring the glass liquid into a preheated mold for molding, and controlling the temperature of the preheated mold within 1200 ℃;
8. and (3) after the glass liquid in the mold is hardened, quickly sending the glass liquid into a furnace which is heated to the temperature near the glass transition temperature in advance for annealing, and cooling to room temperature at the speed of 30 ℃/hour after heat preservation for 3 hours to obtain the high-refractive-index intermediate infrared optical glass.
Example four:
the high-refractive-index intermediate infrared optical glass comprises the following components in parts by mole:
GeO230 parts of Ga2O335 parts of BaO 20 parts of Bi2O325 parts of ZrO215 parts of TiO23 parts of a mixture;
the preparation method of the high-refractive-index mid-infrared optical glass comprises the following steps:
1. selected GeO230 parts of Ga2O335 parts of BaO 20 parts of Bi2O325 parts of ZrO215 parts of TiO23 parts of a mixture; fully grinding the raw materials respectively for later use;
2. grinding GeO2And Ga2O3Mixing, mixing BaO and Bi2O3Mixing for later use;
3. the ground GeO obtained in the step 22And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 800-1000 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the mixed materials, heating to about 1300 ℃ again, adding ZrO2And TiO2Heating to about 1500 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 80 minutes;
4. when the mixture is molten, standing for about 30 minutes, cooling to 750 ℃, introducing high-purity oxygen and stirring for 55 minutes, and ensuring that the temperature is controlled to be about 700 ℃ during stirring;
5. stopping aeration when stirring is finished, and clarifying and homogenizing at 1050 ℃ for about two hours;
6. after homogenization, the temperature is increased to about 1400 ℃ again, and high-speed stirring is carried out;
7. cooling the stirred molten glass to 950 ℃ immediately, then pouring the molten glass into a preheated mold for molding, and controlling the temperature of the preheated mold within 1200 ℃;
8. and (3) after the glass liquid in the mold is hardened, quickly sending the glass liquid into a furnace which is heated to the temperature near the glass transition temperature in advance for annealing, keeping the temperature for 2.5 hours, and then cooling to the room temperature at the speed of 25 ℃/hour to obtain the high-refractive-index intermediate infrared optical glass.
The high-refractive-index intermediate infrared optical glass and the preparation method thereof have the following beneficial effects:
the anti-crystallization capability is strong, and crystallization is not easy to occur in the optical fiber drawing process;
secondly, the infrared transmission range of the glass is 0.65-10 mu m, the transmission rate is about 88%, and the refractive index is more than 3.0;
thirdly, the paint does not contain toxic elements such as lead and cadmium to the environment and human body; the glass has low price, is easy to realize batch production, and is suitable for preparing infrared windows and infrared light path lenses;
fourthly, the glass forming performance of the glass is good, the preparation process is simple, and the processing is easy;
fifthly, the thermal stability is good, and the mechanical strength is high;
sixthly, the glass transition temperature is low, so that the glass is prevented from reacting with the die, and the service life of the die is prolonged; is very suitable for precision compression molding of the intermediate infrared optical element.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (3)
1. A high-refractive-index mid-infrared optical glass is characterized in that: the high-refractive-index intermediate infrared optical glass comprises the following components in parts by mole:
the preparation method of the high-refractive-index mid-infrared optical glass comprises the following steps:
(1) selecting 35-50 parts of GeO225-30 parts of Ga2O312-20 parts of BaO and 15-20 parts of Bi2O33-10 parts of ZrO2And 2-5 parts of Ta2O5(ii) a Fully grinding the raw materials respectively for later use;
(2) the ground GeO2And Ga2O3Mixing, mixing BaO and Bi2O3Mixing for later use;
(3) and (3) grinding the GeO obtained in the step (2)2And Ga2O3Putting the mixed material into a platinum crucible, heating a silicon carbide rod to 800-1000 ℃ in an electric furnace, and adding BaO and Bi2O3Mixing the materials, heating to 1300 deg.C again, adding ZrO2And Ta2O5，Heating to 1500 ℃ to fully melt the materials, fully stirring in the melting process, and heating for 40-90 minutes;
(4) when the mixture is molten, standing for 30 minutes, cooling to 600-800 ℃, introducing high-purity oxygen and stirring for 40-60 min, and ensuring that the temperature is controlled at 700 ℃ during stirring;
(5) stopping ventilation when stirring is finished, and clarifying and homogenizing for two hours at the temperature of 1000-1150 ℃;
(6) after homogenization, the temperature is increased to 1400 ℃ again, and high-speed stirring is carried out;
(7) immediately cooling the stirred glass liquid to 800-1000 ℃, then pouring the glass liquid into a preheated mold for molding, and controlling the temperature of the preheated mold within 1200 ℃;
(8) and after the glass liquid in the mold is hardened, rapidly sending the glass liquid into a furnace which is heated to the glass transition temperature in advance for annealing, preserving heat for 2-3 hours, and then cooling to room temperature at the speed of 20-30 ℃/hour to obtain the infrared optical glass.
2. The high refractive index mid-infrared optical glass as defined in claim 1, wherein: the high-refractive-index intermediate infrared optical glass comprises the following components in parts by mole:
3. the high refractive index mid-infrared optical glass as defined in claim 1, wherein: the high-refractive-index intermediate infrared optical glass has the infrared band transmission range of 0.65-10 mu m, the thermal transition temperature Tg of 400-580 ℃, the high refractive index nd of 3.1-3.68, the thermal expansion coefficient nd of 19-23.8 ppm/DEG C and the Vickers hardness of 2.03-2.78 GPa.
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