CN110117158A - It is a kind of with low-refraction, the optical glass of high transmittance and its preparation method and application - Google Patents
It is a kind of with low-refraction, the optical glass of high transmittance and its preparation method and application Download PDFInfo
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- CN110117158A CN110117158A CN201910444119.0A CN201910444119A CN110117158A CN 110117158 A CN110117158 A CN 110117158A CN 201910444119 A CN201910444119 A CN 201910444119A CN 110117158 A CN110117158 A CN 110117158A
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- glass
- oxide
- optical glass
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- crucible
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- 239000005304 optical glass Substances 0.000 title claims abstract description 29
- 238000002834 transmittance Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 20
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004615 ingredient Substances 0.000 claims abstract description 12
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 11
- 238000003384 imaging method Methods 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000004031 devitrification Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000003595 spectral effect Effects 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000004026 adhesive bonding Methods 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000003723 Smelting Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000013307 optical fiber Substances 0.000 description 13
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000008395 clarifying agent Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- -1 Alkaline-earth metal oxygen Compound Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000382 optic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition 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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- 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
- C03C4/0085—Compositions for glass with special properties for UV-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
- C03C4/00—Compositions for glass with special properties
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear 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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
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)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The present invention provides a kind of optical glass with low-refraction, high transmittance, the raw material containing following weight percent: silica 70%-80%；Diboron trioxide 0-10%；Aluminum oxide 0-5%；Alkali metal oxide 10-20%；Alkaline earth oxide 0-10%；Calcirm-fluoride 0-2%；Titanium dioxide 0-2%；Wherein the weight percent of diboron trioxide and aluminum oxide cannot be 0 simultaneously.The present invention also provides the preparation method and application of above-mentioned optical glass.The optical glass of method preparation of the present invention, refractive index 1.50-1.52,300-1100nm wavelength transmitance >=90%；Its glass smelting molding simultaneously is easy, and the internal flaws such as bubble-free, calculus, striped, glass devitrification resistance energy, chemical stability, ingredient stability are good, and thermal property and material stability meet low numerical aperture fiber and the preparation requirement of imaging fiber element.
Description
Technical field
The present invention relates to optical glass technical fields, and in particular to a kind of optics glass with low-refraction, high transmittance
Glass and its preparation method and application.
Background technique
Optical glass has the high homogeneity in the transparency, chemistry and the physics (structure and performance) of height, has
Specific and accurate optical constant is for manufacturing the lens of optical instrument or mechanical system, prism, reflecting mirror, window, optical fiber
Deng critical material, played an important role in photoelectric technology industry.Wherein low-refraction/high transmittance optical glass because
Its with lower refractive index and higher spectral transmittance, be low numerical aperture or middle numerical aperture special optical fiber and optical fiber at
The basic material of element.
The prior art mostly mixes the oxides such as a certain amount of boron oxide, germanium oxide in quartz glass, with quartz glass
Refractive index difference is limited, is only capable of preparing the special optical fiber (0.22 or so) of extremely low numerical aperture.And high-quality silica fibre is pre-
Stick preparation difficulty processed is big, expensive, is only capable of production simple optical fiber, can not be prepared into bulk-optic element.
And the imaging fibers element such as conventional optical fibre face plate, be by the regularly arranged fusion of tens million of glass optical fibers and
At, but numerical aperture is greater than 0.65, is unable to satisfy the application requirement for requiring the low numerical aperture of imaging fiber element (0.1-0.3).
Formula is calculated according to numerical aperture, in order to prepare the optical fiber and fibre faceplate of numerical aperture 0.1-0.3, optical glass
Refractive index should be between 1.50-1.52.Meanwhile with the increase of optical fiber specific surface area, to fiber optic materials atmospheric corrosion resistance
Capability Requirement is higher and higher, prevents the defect formed after corrosion from impacting to fibre loss and intensity.In addition, low numerical aperture
Multiple thermal process is undergone in optical fiber and imaging fiber element preparation process, it is desirable that substrate glass material must have excellent resist
Crystallization property and ingredient stability are avoided causing the component diffusions such as material crystallization, split-phase or alkali metal ion in preparation process, be led
Fibre loss increase, image quality is caused to be deteriorated.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide it is a kind of with low-refraction, high transmittance optical glass and
Preparation method and application.
To achieve the above object, the technical scheme adopted by the invention is that:
A kind of optical glass with low-refraction, high transmittance, the raw material containing following following weight percent: dioxy
SiClx 70%-80%；Diboron trioxide 0-10%；Aluminum oxide 0-5%；Alkali metal oxide 10-20%；Alkaline-earth metal oxygen
Compound 0-10%；Calcirm-fluoride 0-2%；Titanium dioxide 0-2%；Wherein the weight percent of diboron trioxide and aluminum oxide is not
It can simultaneously be 0.
Further, wherein the alkali metal oxide includes at least one of lithia, sodium oxide molybdena or potassium oxide.
Further, wherein the alkaline earth oxide includes at least one of magnesia, calcium oxide or barium monoxide.
Further, wherein being also lower than 5 ‰ three oxidations two in the optical glass comprising total amount by weight percentage
At least one of antimony, sodium chloride, sodium bromide, sodium fluoride, potassium fluoride, potassium chloride or potassium bromide；It is mainly as clarification dosage form
Formula introduces, and facilitates the bubble discharge in glass melting process.
Further, wherein the optical glass has the following performance, refractive index: 1.50~1.52；Spectral transmittance: thick
Spend the sheet glass of 10mm, spectral transmittance >=90% within the scope of 300-1100nm；Linear expansion coefficient are as follows: (80~90) × 10-7/
℃；Glass transformation temperature: 520-570 DEG C；Glass transition temperature: 600-650 DEG C；Glass softening point (viscosity 107.6When Pas
Corresponding temperature): 700-760 DEG C；Devitrification resistance energy: 850-900 DEG C of heat preservation does not generate crystallization in 3 hours in Muffle furnace；It is moisture resistance
Stability: 1 class；Acid-resistant stability: 1 class；Ingredient stability: with ZK9 glass gluing, keeping the temperature 1 hour at 700 DEG C, interface alkali gold
Belong to ion diffusion and is less than or equal to 1%.
The present invention also provides a kind of above-mentioned preparation methods with low-refraction, the optical glass of high transmittance, including with
Lower step:
1) above-mentioned raw materials are weighed according to formula ratio, is uniformly mixed and obtains batch；
2) at 1400-1480 DEG C by batch by carrying out melted, each feeding interval in one or many addition crucibles
Time is -1 hour 10 minutes；
3) it is warming up to 1450-1500 DEG C after the completion of charging and carries out clarification 5-10 hours；
4) 1250-1350 DEG C of heat preservation is cooled to after clarifying to be homogenized for 3-5 hours；
5) by glass metal, moulding by casting is glass bar in a mold after being homogenized；
6) molding glass bar keeps the temperature 2-3 hours at 500-600 DEG C, and then power-off is come out of the stove after being annealed to room temperature.
Further, wherein in step 1), in step 1), in the batch, silica is with quartz sand or crystal powder
Form introduce, diboron trioxide introduces in the form of boric acid, and alkali metal oxide is in the form of its carbonate and/or nitrate
It introduces, alkaline earth oxide is introduced in the form of its carbonate and/or nitrate.
Further, wherein in step 1), the batch also contains antimony oxide, sodium chloride, sodium bromide, fluorination
At least one of sodium, potassium fluoride, potassium chloride or potassium bromide.
Further, wherein in step 2), the crucible is clay crucible, alumina crucible, magnesia crucible, quartzy earthenware
Crucible or platinum crucible.
Further, wherein crucible in the melted process (adding raw materials into crucible, just started melting process)
Interior to keep weak oxide atmosphere, weak oxide atmosphere refers to that oxygen partial pressure is greater than the partial pressure of oxygen in atmosphere in atmosphere, described weak
Oxygen partial pressure is greater than 30kPa in oxidizing atmosphere.
The present invention also provides a kind of imaging fiber element, the imaging fiber element includes above-mentioned optical glass.
The beneficial effects of the present invention are: optical glass prepared by the present invention, refractive index 1.50-1.52,300-
1100nm wavelength transmitance >=90%；Its glass smelting molding simultaneously is easy, and the internal flaws such as bubble-free, calculus, striped are passed through
Otherwise multiple heat treatment process will lead to optical signal and serious scattering occur, reduce transmitance without generating crystallization or split-phase
And imaging definition.In addition the chemical stability of the glass, ingredient stability are good, and ZK9 glass gluing, and heat preservation 1 is small at 700 DEG C
When, alkali metal ion diffusion in interface is less than or equal to 1%；It can guarantee in this way in processes such as drawing optical fibers, fiber array hot melt pressures
In, the ingredient between fibre core and cortex glass is not spread, and is prevented core skin interface from forming refractive index gradient, is improved optical signal
Total reflectivity reduces interface loss.In addition the thermal property of the glass and ingredient stability can meet low numerical aperture fiber and
The preparation of imaging fiber element requires.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The materials, reagents and the like used in the following examples is commercially available.
The formula composition and physical chemistry with low-refraction, the optical glass of high transmittance of 1-8 of the embodiment of the present invention
Performance is shown in Table 1.
Wherein, refractive index is tested according to GB/T 7962.1-2010；The coefficient of expansion, transition temperature, softening temperature, softening point
It is tested according to GB/T 7962.16-2010；Transmitance is tested according to GB/T 7962.12-2010；Moisture resistance stability is according to GB/T
7962.15-2010 test；Acid-resistant stability is tested according to GB/T 7962.14-2010；Devitrification resistance energy test method is by glass
Glass sample is added in Muffle furnace, is warming up to 850-900 DEG C, keeps the temperature 3 hours, subsequent Temperature fall to room temperature is micro- with 6-10 times
Whether crystallization or split-phase are occurred in sem observation glass；Ingredient stability test method is closely to paste glass sample and ZK9 glass
Close, lay flat into Muffle furnace, be heated to 700 DEG C, keep the temperature 1 hour, with EDS (photoelectron spectrograph) detection interface alkali metal from
The changes of contents of son.
Table 1
The optical glass that can be seen that 1-8 of the embodiment of the present invention from the data of table 1 has the following performance, refractive index: 1.50
~1.52；Spectral transmittance: the sheet glass of thickness 10mm, spectral transmittance >=90% within the scope of 300-1100nm；Line expansion
Coefficient are as follows: (80~90) × 10-7/℃；Glass transformation temperature: 520-570 DEG C；Glass transition temperature: 600-650 DEG C；Glass is soft
Change point (viscosity 107.6Corresponding temperature when Pas): 700-760 DEG C；Devitrification resistance energy: the 850-900 DEG C of guarantor in Muffle furnace
Temperature does not generate crystallization in 3 hours；Moisture resistance stability: 1 class；Acid-resistant stability: 1 class；Ingredient stability: with ZK9 glass gluing, 700
1 hour is kept the temperature at DEG C, alkali metal ion diffusion in interface is less than or equal to 1%.As it can be seen that the optical glass of 1-8 of the embodiment of the present invention is equal
Low numerical aperture fiber can be met and the preparation of imaging fiber element requires.
In the present invention, SiO2It is the main body that glass forms skeleton, is the ingredient to play a major role in glass skeleton.With weight
Percentages, SiO2Content is lower than 70%, is not easy to obtain the glass of low-refraction, while the chemically-resistant that can reduce glass is stablized
Property；SiO2When content is higher than 80%, the high-temperature viscosity of glass be will increase, and cause glass smelting temperature excessively high.B2O3It is also glass shape
At oxide, and the ingredient of glass skeleton is constituted, while being a kind of cosolvent for reducing glass smelting viscosity again, and reduce
The main component of glass refraction.Boron oxygen trihedral [BO3] and boron oxygen tetrahedron [BO4] it is structural component, at different conditions boron
It may be with boron oxygen trihedral [BO3] or boron oxygen tetrahedron [BO4] exist, in high temperature melting condition, it is generally more difficult to form boron oxygen four
Face body, and can only existing in a manner of boron oxygen trihedral, but in low temperature, under certain condition B3+Have and captures free oxygen formation four
The trend of face body makes close structure and improves the low temperature viscosity of glass, but high temperature reduces glass viscosity and low temperature mentions since it has
The characteristic of high glass viscosity.By weight percentage, B2O3Content be greater than 10%, the coefficient of expansion of glass can be reduced, made simultaneously
The split-phase of glass, which is inclined to, to be increased, and is not easy to match draw optical fibers with glass of high refractive index.
Al2O3Belong to the intermediate oxide of glass, Al3+There are two types of co-ordination states, that is, are located in tetrahedron or octahedron,
When oxygen is enough in glass, aluminum-oxygen tetrahedron [AlO is formed4], continuous network is formed with oxygen-octahedron；When oxygen in glass
When insufficient, alumina octahedral [AlO is formed6], it is in for network outer body in the hole of silica structure network, so centainly containing
Measure range in can and SiO2The main body formed as glass network.By weight percentage, Al2O3Content is greater than 5% can be significant
The high-temperature viscosity for increasing glass, increases the glass melting temperature of glass.Therefore, by weight percentage, Al2O3Content be 0-
5%, preferably 1%-3%.
Further, in order to promote the chemistry and ingredient stability of glass, in addition to SiO2Except Network former, oxidation
The content of boron and aluminium oxide cannot be zero simultaneously.
Alkali metal oxide R2O includes lithia, sodium oxide molybdena, potassium oxide, mainly network outer body, with weight percent
Meter, content are lower than 10%, and glass melting temperature is very high, intensity difference, cracky.By weight percentage, alkali metal oxide R2O
Content be higher than 20%, glass expansion coefficient is too high, softening temperature is low, be not suitable for fiber draw process requirement.
Alkaline earth oxide RO includes magnesia, calcium oxide, barium monoxide, and as network outer body.With weight percent
Than meter, the content of alkaline earth oxide RO is more than 10%, will increase the tendency towards devitrification of glass, reduces refractive index.
CaF2It is introduced into glass as clarifying agent, the discharge of Bubbles in Glass can be promoted.CaF2Content be more than 2%, meeting
Reduce the stability of glass.
TiO2Be also as clarifying agent introduce, while can also appropriate adjustment glass refractive index, reduce dispersion.TiO2Contain
Amount can make glass form yellowish red color more than 2%, reduce transmitance.
The clarifying agent being often used in optical glass melting process there are also antimony oxide, sodium chloride, sodium bromide, sodium fluoride,
Potassium fluoride, potassium chloride or potassium bromide, by weight percentage total amount are lower than 5 ‰, are otherwise for the refractive index of glass, expansion
Number, transmitance can adversely affect.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of optical glass with low-refraction, high transmittance, which is characterized in that the original containing following weight percent
Material: silica 70%-80%；Diboron trioxide 0-10%；Aluminum oxide 0-5%；Alkali metal oxide 10-20%；Alkali
Soil metal oxide 0-10%；Calcirm-fluoride 0-2%；Titanium dioxide 0-2%；The wherein weight of diboron trioxide and aluminum oxide
Percentage cannot be 0 simultaneously.
2. optical glass as described in claim 1, which is characterized in that the alkali metal oxide includes lithia, sodium oxide molybdena
Or at least one of potassium oxide.
3. optical glass as described in claim 1, which is characterized in that the alkaline earth oxide includes magnesia, oxidation
At least one of calcium or barium monoxide.
4. optical glass as described in claim 1, which is characterized in that also comprising by weight percentage in the optical glass
At least one in antimony oxide of the total amount lower than 5 ‰, sodium chloride, sodium bromide, sodium fluoride, potassium fluoride, potassium chloride or potassium bromide
Kind.
5. optical glass as described in claim 1, which is characterized in that the optical glass has the following performance, refractive index:
1.50~1.52；Spectral transmittance: the sheet glass of thickness 10mm, spectral transmittance >=90% within the scope of 300-1100nm；Line
The coefficient of expansion are as follows: (80~90) × 10-7/℃；Glass transformation temperature: 520-570 DEG C；Glass transition temperature: 600-650 DEG C；Glass
Glass softening point (viscosity 107.6Corresponding temperature when Pas): 700-760 DEG C；Devitrification resistance energy: the 850-900 in Muffle furnace
DEG C heat preservation does not generate crystallization in 3 hours；Moisture resistance stability: 1 class；Acid-resistant stability: 1 class；Ingredient stability: with ZK9 glass gluing,
1 hour is kept the temperature at 700 DEG C, alkali metal ion diffusion in interface is less than or equal to 1%.
6. a kind of described in any item preparation methods with low-refraction, the optical glass of high transmittance of claim 1-5,
It is characterized in that, comprising the following steps:
1) above-mentioned raw materials are weighed according to formula ratio, is uniformly mixed and obtains batch；
2) at 1400-1480 DEG C by batch by carrying out melted, each feeding interval time in one or many addition crucibles
It is -1 hour 10 minutes；
3) it is warming up to 1450-1500 DEG C after the completion of charging and carries out clarification 5-10 hours；
4) 1250-1350 DEG C of heat preservation is cooled to after clarifying to be homogenized for 3-5 hours；
5) by glass metal, moulding by casting is glass bar in a mold after being homogenized；
6) molding glass bar keeps the temperature 2-3 hours at 500-600 DEG C, and then power-off is come out of the stove after being annealed to room temperature.
7. preparation method as claimed in claim 6, which is characterized in that in step 1), in the batch, silica is with stone
The form of sand or crystal powder introduces, and diboron trioxide introduces in the form of boric acid, alkali metal oxide with its carbonate and/or
The form of nitrate introduces, and alkaline earth oxide is introduced in the form of its carbonate and/or nitrate.
8. preparation method as claimed in claim 7, which is characterized in that in step 1), the batch also contains three oxidations two
At least one of antimony, sodium chloride, sodium bromide, sodium fluoride, potassium fluoride, potassium chloride or potassium bromide.
9. preparation method as claimed in claim 6, which is characterized in that in step 2), the crucible is clay crucible, aluminium oxide
Crucible, magnesia crucible, silica crucible or platinum crucible；It is described be melted during weak oxide atmosphere, institute are kept in crucible
It states oxygen partial pressure in weak oxide atmosphere and is greater than 30kPa.
10. a kind of imaging fiber element, which is characterized in that the imaging fiber element includes described in any one of claim 1-5
Optical glass.
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| CN201910444119.0A CN110117158A (en) | 2019-05-27 | 2019-05-27 | It is a kind of with low-refraction, the optical glass of high transmittance and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393023A (en) * | 2020-04-22 | 2020-07-10 | 中国建筑材料科学研究总院有限公司 | High-definition optical fiber image inverter and preparation method and application thereof |
| CN113955937A (en) * | 2021-11-26 | 2022-01-21 | 中建材光芯科技有限公司 | Chemically-strengthened optical fiber panel and preparation method thereof |
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| WO1980002140A1 (en) * | 1979-04-02 | 1980-10-16 | Western Electric Co | Optical fibers containing aluminum metaphosphate |
| US20050100305A1 (en) * | 2002-10-02 | 2005-05-12 | Ralf Domres | Optical fibers made from multicomponent glass |
| CN202379886U (en) * | 2011-11-22 | 2012-08-15 | 中国建筑材料科学研究总院 | Low refractive index environment-friendly glass for fiber optic faceplate |
| CN106517772A (en) * | 2016-10-25 | 2017-03-22 | 中国建筑材料科学研究总院 | Low-refractive glass applied to drawing formation preparation of optical fiber faceplate and preparation method thereof |
| CN109455928A (en) * | 2018-12-28 | 2019-03-12 | 山东省科学院激光研究所 | Borosilicate glass and its preparation method and application |
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| WO1980002140A1 (en) * | 1979-04-02 | 1980-10-16 | Western Electric Co | Optical fibers containing aluminum metaphosphate |
| US20050100305A1 (en) * | 2002-10-02 | 2005-05-12 | Ralf Domres | Optical fibers made from multicomponent glass |
| CN202379886U (en) * | 2011-11-22 | 2012-08-15 | 中国建筑材料科学研究总院 | Low refractive index environment-friendly glass for fiber optic faceplate |
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| CN111393023A (en) * | 2020-04-22 | 2020-07-10 | 中国建筑材料科学研究总院有限公司 | High-definition optical fiber image inverter and preparation method and application thereof |
| CN111393023B (en) * | 2020-04-22 | 2022-07-26 | 中国建筑材料科学研究总院有限公司 | High-definition optical fiber image inverter and preparation method and application thereof |
| CN113955937A (en) * | 2021-11-26 | 2022-01-21 | 中建材光芯科技有限公司 | Chemically-strengthened optical fiber panel and preparation method thereof |
| CN113955937B (en) * | 2021-11-26 | 2023-11-07 | 中建材光芯科技有限公司 | Chemically strengthened optical fiber panel and preparation method thereof |
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