CN113415991A - Optical glass and optical element - Google Patents
Optical glass and optical element Download PDFInfo
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- CN113415991A CN113415991A CN202110857806.2A CN202110857806A CN113415991A CN 113415991 A CN113415991 A CN 113415991A CN 202110857806 A CN202110857806 A CN 202110857806A CN 113415991 A CN113415991 A CN 113415991A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 75
- 230000003287 optical effect Effects 0.000 title claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 36
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 36
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 19
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000008395 clarifying agent Substances 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910006735 SnO2SnO Inorganic materials 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002597 diffusion-weighted imaging Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 22
- 238000013461 design Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000004031 devitrification Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 230000005499 meniscus Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- -1 platinum ions Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052726 zirconium 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
- 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
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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 invention provides an optical glass, which comprises the following components in percentage by mole: SiO 22:10~30%;B2O3:40~60%;Al2O3:5~20%;La2O3:5~20%;Y2O3: 1 to 15% of (SiO)2+Al2O3)/B2O30.3 to 1.1. Through reasonable component design, the optical glass obtained by the invention has excellent chemical stability and higher hardness while having the expected refractive index and Abbe number.
Description
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.65-1.70 and an Abbe number of 51-59.
Background
In recent years, with the development of digital camera devices, image pickup devices, projection devices, and in-vehicle devices, etc., the demand for optical elements has been increasing, and development and production of optical glasses with higher performance have been demanded. In the optical glass for manufacturing optical elements, the market demand for medium refractive index low dispersion optical glass, which can correct chromatic aberration and miniaturize an optical system, and has a refractive index of 1.65 to 1.70 and an abbe number of 51 to 59, is increasing. Since monitoring cameras, vehicle-mounted cameras and the like, which are in increasing demand in recent years, are often used outdoors, existing glass imaging elements are often exposed to weather or sand and dust environments, and in the case of long-term use, glass is required to have excellent chemical stability and high hardness to improve the service life of monitoring equipment and vehicle-mounted equipment.
Disclosure of Invention
The invention aims to provide optical glass with excellent chemical stability and high hardness.
The technical scheme adopted by the invention for solving the technical problem is as follows:
optical glass, the components of which, expressed in molar percentages, contain: SiO 22:10~30%;B2O3:40~60%;Al2O3:5~20%;La2O3:5~20%;Y2O3: 1 to 15% of (SiO)2+Al2O3)/B2O30.3 to 1.1.
Further, the optical glass comprises the following components in percentage by mole: gd (Gd)2O3: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or CaO: 0 to 10 percent; and/or SrO: 0 to 10 percent; and/or BaO: 0 to 10 percent; and/or Zr02: 0 to 5 percent; and/or Ta2O5: 0 to 5 percent; and/or Nb2O5: 0 to 5 percent; and/or ZnO: 0 to 10 percent; and/or Rn20: 0 to 10 percent; and/or a clarifying agent: 0 to 1%, of the total amount of Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
Optical glass, the composition of which, expressed in mole percent, is represented by SiO2:10~30%;B2O3:40~60%;Al2O3:5~20%;La2O3:5~20%;Y2O3:1~15%;Gd2O3:0~10%;MgO:0~10%;CaO:0~10%;SrO:0~10%;BaO:0~10%;Zr02:0~5%;Ta2O5:0~5%;Nb2O5:0~5%;ZnO:0~10%;Rn20: 0 to 10 percent; a clarifying agent: 0 to 1% of a component of (SiO)2+Al2O3)/B2O30.3 to 1.1, the Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
Further, the optical glass has the components expressed by mole percent, and satisfies more than one of the following 5 conditions:
1)(SiO2+Al2O3)/B2O30.4 to 1.0;
2)Al2O3/Ln2O30.3 to 1.5;
3)Ln2O3the/RO is more than 2.0;
4) RO is 0-15%;
5)Ln2O38 to 30%, wherein RO is the total content of MgO, CaO, SrO and BaO, Ln2O3Is La2O3、Y2O3And Gd2O3The total content of (a).
Further, the optical glass comprises the following components in mol percentage: SiO 22: 12-25%; and/or B2O3: 42-55%; and/or Al2O3: 7-18%; and/or La2O3: 8-18%; and/or Y2O3: 2-12%; and/or Gd2O3: 0 to 5 percent; and/or MgO: 0-8%; and/or CaO: 0-8%; and/or SrO: 0-8%; and/or BaO: 0-8%; and/or Zr02: 0 to 3 percent; and/or Ta2O5: 0 to 3 percent; and/or Nb2O5: 0 to 3 percent; and/or ZnO: 0 to 5 percent; and/or Rn20: 0 to 5 percent; and/or a clarifying agent: 0 to 0.5%, the Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
Further, the optical glass has the components expressed by mole percent, and satisfies more than one of the following 5 conditions:
1)(SiO2+Al2O3)/B2O30.5 to 0.8;
2)Al2O3/Ln2O30.4 to 1.2;
3)Ln2O3the/RO is more than 3.0;
4) RO is 0-10%;
5)Ln2O310 to 26% of a total amount of RO, Ln, MgO, CaO, SrO and BaO2O3Is La2O3、Y2O3And Gd2O3The total content of (a).
Further, the optical glass comprises the following components in mol percentage: SiO 22: 15-22%; and/or B2O3: 45-52 percent; and/or Al2O3: 8-15%; and/or La2O3: 10-16%; and/or Y2O3: 3-10%; and/or Gd2O3: 0-2%; and/or MgO: 0-6%; and/or CaO: 0-6%; and/or SrO: 0-6%; and/or BaO: 0-6%; and/or Zr02: 0 to 1 percent; and/or Ta2O5: 0 to 1 percent; and/or Nb2O5: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or Rn20: 0-2%; and/or a clarifying agent: 0 to 0.1%, the Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
Further, the optical glass has the components expressed by mole percent, and satisfies more than one of the following 4 conditions:
1)Al2O3/Ln2O30.5 to 0.8;
2)Ln2O3the/RO is more than 4.0;
3) RO is 0-8%;
4)Ln2O315 to 22%, wherein RO is the total content of MgO, CaO, SrO and BaO, Ln2O3Is La2O3、Y2O3And Gd2O3The total content of (a).
Further, the refractive index n of the optical glassd1.65 to 1.70, preferably a refractive index nd1.66 to 1.69, and more preferably a refractive index ndIs 1.67 to 1.68, and has an Abbe number vd51 to 59, preferably Abbe number vdIs 52 to 58, and the Abbe number v is more preferabledIs 53 to 57.
Further, the stability of the optical glass against water action DWIs 2 or more, preferably 1; and/or stability against acid action DAIs 4 or more, preferably 3 or more; and/or Knoop hardness HKIs 650 x 107Pa or more, preferably 670X 107Pa is above; and/or a density p of 3.70g/cm3Hereinafter, it is preferably 3.60g/cm3The following.
The glass preform is made of the optical glass.
And the optical element is made of the optical glass or the glass prefabricated member.
An optical device comprising the above optical glass and/or comprising the above optical element.
The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has excellent chemical stability and higher hardness while having the expected refractive index and Abbe number.
Detailed Description
The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the following, the optical glass of the present invention is sometimes simply referred to as glass.
[ optical glass ]
The ranges of the respective components (components) of the optical glass of the present invention are explained below. In the present invention, unless otherwise specified, the contents and total contents of the respective components are all expressed in terms of mole percent (mol%), that is, the contents and total contents of the respective components are expressed in terms of mole percent relative to the total amount of glass matter converted into the composition of oxides. Here, the term "composition in terms of oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted into oxides, the total molar amount of the oxides is 100%.
Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
SiO2Is an essential component of the present invention by containing more than 10% SiO2To improve the processability and chemical stability of the glass. Thus, SiO2The content of (b) is 10% or more, preferably 12% or more, more preferably 15% or more. On the other hand, by mixing SiO2The content of (b) is limited to 30% or less, and a larger refractive index can be easily obtained, and deterioration of glass meltability and excessive increase in viscosity can be suppressed. Thus, SiO2The content of (b) is 30% or less, preferably 25% or less, more preferably 22% or less.
B2O3Is an essential component of the present invention, by containing more than 40% of B2O3This has the effect of improving the meltability of glass and resistance to devitrification. Thus, B2O3The content of (b) is 40% or more, preferably 42% or more, and more preferably 45% or more. On the other hand, by mixing B2O3The content of (b) is limited to 60% or less, and deterioration of chemical stability of the glass can be suppressed. Thus, B2O3The content of (b) is 60% or less, preferably 55% or less, more preferably 52% or less.
Al2O3Is an essential component of the present invention, has the effect of improving processability, resistance to devitrification and chemical stability, and Al in the present invention2O3The content of the component (B) is 5% or more, preferably 7% or more, more preferably 8% or more. Particularly, the SiO content is more than 15%2When the component (C) is contained, 8% or more of Al is added2O3Can inhibit SiO2The devitrification due to the component (B) gives a glass excellent in devitrification resistance. On the other hand, by mixing Al2O3The content of the component is limited to 20% or less, and excessive Al content can be prevented2O3Deterioration of resistance to devitrification and reduction of refractive index due to the component. Thus, Al2O3The content of the component (B) is 20% or less, preferably 18% or less, more preferably 15% or less.
In some embodiments of the invention, the composition is prepared by reacting (SiO)2+Al2O3)/B2O3The value of (A) is limited to more than 0.3, so that the chemical stability and hardness of the glass can be improved; on the other hand, by mixing (SiO)2+Al2O3)/B2O3The limit of 1.1 or less improves the glass processability, and suppresses the deterioration of the melting property of the glass raw material and the excessive increase of the viscosity. Therefore, (SiO) is preferable2+Al2O3)/B2O30.3 to 1.1, more preferably (SiO)2+Al2O3)/B2O30.4 to 1.0, and more preferably (SiO)2+Al2O3)/B2O30.5 to 0.8.
La2O3Has the effect of improving the refractive index and Abbe number of the glass, and contains more than 5% of La2O3To obtain the above effects, La is preferable2O3The content of (A) is 8% or more, more preferably La2O3The content of (A) is more than 10%. On the other hand, by mixing La2O3The content of (2) is limited to 20% or less, and the stability of the glass can be prevented from being lowered. Thus, La2O3The content of (A) is 20% or less, preferably 18% or less, more preferably 16% or less。
Will Y2O3The content of (b) is limited to 1% or more, and the specific gravity of the glass can be reduced compared with other rare earth components while suppressing the increase in the material cost of the glass while maintaining a high refractive index and a high Abbe number. On the other hand, by mixing Y2O3The content of the component (A) is limited to 15% or less, and the devitrification resistance and the chemical stability of the glass can be prevented from being lowered. Thus, Y2O3The content of the component (A) is 1 to 15%, preferably 2 to 12%, more preferably 3 to 10%.
Gd2O3The refractive index and Abbe number of the glass may be increased, in some embodiments of the invention, by the incorporation of Gd2O3The content of (B) is limited to 10% or less, and the increase of the specific gravity of the glass can be suppressed. Thus, Gd2O3The content of (b) is 10% or less, preferably 5% or less, more preferably 2% or less.
In some embodiments of the invention, the La is prepared by subjecting La2O3、Y2O3And Gd2O3Total content Ln of2O3By controlling the refractive index and Abbe number of the glass to 8% or more, the refractive index and Abbe number of the glass can be increased, and the glass having a desired refractive index and Abbe number can be easily obtained. Thus, Ln2O3Preferably 8% or more, more preferably 10% or more, and still more preferably 15% or more. On the other hand, by mixing Ln2O3The content of (b) is limited to 30% or less, and the liquid phase temperature of the glass can be lowered to prevent devitrification of the glass and improve the chemical stability of the glass. Thus, Ln2O3The content of (b) is preferably 30% or less, more preferably 26% or less, and further preferably 22% or less.
In some embodiments, Al is added2O3/Ln2O3The chemical stability and hardness of the glass are improved by controlling the content of the glass to be more than 0.3; on the other hand, by mixing Al2O3/Ln2O3The glass processability can be improved by limiting the glass to 1.5 or less. Therefore, Al is preferable2O3/Ln2O30.3 to 1.5, furtherPreferably Al2O3/Ln2O30.4 to 1.2, and further preferably Al2O3/Ln2O30.5 to 0.8.
MgO can improve the low-temperature melting property of the glass, and by setting the content of MgO to 10% or less, deterioration in chemical stability due to the inclusion of an excessive MgO component can be suppressed. Therefore, the content of the MgO component is 10% or less, preferably 8% or less, and more preferably 6% or less.
While CaO can improve the low-temperature fusibility of the glass, limiting the content of CaO to 10% or less can suppress deterioration of chemical stability due to the excessive content of CaO component. Therefore, the content of the CaO component is 10% or less, preferably 8% or less, and more preferably 6% or less.
SrO can improve the low-temperature melting property of the glass, and on the other hand, by limiting the content of the SrO component to 10% or less, deterioration in chemical stability due to the excessive SrO component can be suppressed. Therefore, the content of the SrO component is 10% or less, preferably 8% or less, and more preferably 6% or less.
BaO can improve the low-temperature melting property of the glass, and on the other hand, by limiting the content of the BaO component to 10% or less, deterioration of chemical stability due to the excessive BaO component can be suppressed. Therefore, the content of the BaO component is 10% or less, preferably 8% or less, and more preferably 6% or less.
In some embodiments of the present invention, by limiting the total content R0 of MgO, CaO, SrO, and BaO to 15% or less, deterioration in chemical stability of the glass due to the excessive content of R0 can be suppressed. Therefore, the content of R0 is preferably 15% or less, more preferably 10% or less, and still more preferably 8% or less.
In some embodiments, by mixing Ln2O3the/RO is controlled to be more than 2.0, and the chemical stability of the glass can be improved. Therefore, Ln is preferable2O3The ratio of/RO is 2.0 or more, and Ln is more preferable2O3The ratio of/RO is 3.0 or more, and Ln is more preferable2O3The ratio of/RO is 4.0 or more.
Zr02The refractive index and Abbe number of the glass can be improved, and the processability of the glass can be improved. On the other hand, by adding Zr02The content of (3) is limited to 5% or less, and the content of excess Zr0 can be reduced2Resulting in devitrification of the glass. Thus, Zr02The content of (b) is 5% or less, preferably 3% or less, more preferably 1% or less.
Ta2O5Can improve the refractive index and the anti-devitrification performance of the glass. On the other hand, by using expensive Ta2O5The composition is limited to 5% or less, and the raw material cost of the glass can be reduced. Thus, Ta2O5The content of (b) is 5% or less, preferably 3% or less, more preferably 1% or less. Ta may not be contained from the viewpoint of cost reduction2O5。
Nb2O5Can increase the refractive index of the glass by adding Nb2O5The content of (B) is limited to 5% or less, and the content of excess Nb can be reduced2O5Devitrification due to the component(s) and a decrease in the transmittance of the glass to visible light (particularly, a wavelength of 500nm or less) can be suppressed. Thus, Nb2O5The content of (b) is 5% or less, preferably 3% or less, more preferably 1% or less.
While ZnO can improve the low-temperature melting property of the glass, by limiting the content of ZnO to 10% or less, the decrease in abbe number caused by the excessive content of ZnO can be suppressed. Therefore, the ZnO content is 10% or less, preferably 5% or less, and more preferably 1% or less.
Rn20(Rn20 is Li2O、Na2O、K2One or more kinds of O) can adjust the refractive index of the glass and improve the meltability of the glass. By mixing Rn2The content of 0 is controlled to 10% or less, and excess Rn due to the inclusion can be suppressed20 component, and deterioration of chemical stability. Thus, Rn2The content of 0 is 10% or less, preferably 5% or less, and more preferably 2% or less.
Clarifying with 0-1%The agent can improve the clarification effect of glass, and Sb can be adopted in the invention2O3、SnO2SnO and CeO2As a clarifying agent. However, the present invention has a reasonable formulation design, and therefore, the present invention preferably contains 0 to 0.5% of a clarifying agent, more preferably 0 to 0.1% of a clarifying agent, and even more preferably no clarifying agent, because of its excellent clarifying effect and excellent air bubble degree.
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
In order to achieve environmental friendliness, the optical glass of the present invention does not contain As2O3And PbO. Although As2O3Has the effects of eliminating bubbles and better preventing the glass from coloring, but As2O3The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As2O3All cause environmental pollution.
"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (n) of optical glassd) And Abbe number (v)d) The test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n) of the optical glass of the present inventiond) The lower limit of (b) is 1.65, preferably 1.66, more preferably 1.67. In some embodiments, the refractive index (n) of the optical glass of the present inventiond) The upper limit of (a) is 1.70, preferably the upper limit is 1.69, and more preferably the upper limit is 1.68.
In some embodiments, the Abbe number (v) of the optical glass of the present inventiond) The lower limit of (2) is 51, preferably 52, and more preferably 53. In some embodiments, the Abbe number (v) of the optical glass of the present inventiond) The upper limit of (3) is 59, preferably 58, more preferably 57.
< stability against Water action >
Stability to Water of optical glass (D)W) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the optical glass of the present invention has stability to water effects (D)W) Is 2 or more, preferably 1.
< stability against acid Effect >
Stability of acid resistance of optical glasses (D)A) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the stability to acid action of the optical glasses of the invention (D)A) Is in 4 or more types, preferably 3 or more typesThe above.
< Knoop hardness >
Knoop hardness (H) of optical glassK) The test was carried out according to the test method specified in GB/T7962.18-2010.
In some embodiments, the Knoop hardness (H) of the optical glasses of the present inventionK) Is 650 x 107Pa or more, preferably 670X 107Pa or above.
< Density >
The density (. rho.) of the optical glass was measured according to the test method specified in GB/T7962.20-2010.
In some embodiments, the optical glass of the present invention has a density (. rho.) of 3.70g/cm3Hereinafter, it is preferably 3.60g/cm3The following.
[ method for producing optical glass ]
The method for manufacturing the optical glass comprises the following steps: the glass of the invention can be produced by adopting conventional raw materials and processes, including but not limited to using carbonate, nitrate, sulfate, hydroxide, oxide, fluoride and the like as raw materials, mixing the raw materials according to a conventional method, putting the mixed furnace charge into a smelting furnace (such as a platinum or platinum alloy crucible) at 1250-1350 ℃ for smelting, obtaining homogeneous molten glass without bubbles and undissolved substances after clarification and homogenization, casting the molten glass in a mould and annealing.
The glass of the invention can also be produced by adopting a secondary smelting mode, namely, the mixture of the raw materials is firstly put into a quartz, alumina or zirconium crucible for smelting, the clinker is prepared after the smelting is finished, and then the clinker is put into a platinum or platinum alloy crucible for smelting, so that the required high-quality glass is obtained.
Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Glass preform and optical element
The glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention. The glass prefabricated member of the invention has the characteristics of medium refractive index and low dispersion; various optical elements such as lenses and prisms having high optical values can be provided. By having such an intermediate refractive index, a large amount of light refraction can be obtained even when the optical element is thinned. Further, by having such low dispersion, it is possible to reduce the deviation of focus (chromatic aberration) due to the wavelength of light when used as a single lens. Therefore, the optical glass of the present invention is useful in optical design, and particularly in the case of constituting an optical system, it is possible to realize miniaturization of the optical system while realizing high imaging characteristics and the like, and it is possible to expand the degree of freedom in optical design.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
Further, since the prism has a relatively high refractive index, by combining the prism with an imaging optical system and bending the optical path to direct the prism in a desired direction, a compact and wide-angle optical system can be realized.
[ optical instruments ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like. The optical glass has excellent chemical stability, and is particularly suitable for being applied to the fields of vehicle-mounted monitoring, security protection and the like.
In order to further understand the technical solution of the present invention, examples of the optical glass of the present invention will be described below. It should be noted that these examples do not limit the scope of the present invention.
Examples
< example of optical glass >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 1 to 2 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2. In the following table (SiO)2+Al2O3)/B2O3Is denoted by K1; ln2O3Is denoted by K2; al (Al)2O3/Ln2O3Is denoted by K3; the value of RO is denoted by K4; ln2O3The value of/RO is denoted K5.
TABLE 1
TABLE 2
< glass preform example >
Various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens and a plano-concave lens, and preforms such as prisms were produced from the glasses obtained in examples 1 to 20 of optical glass by means of polishing or press molding such as reheat press molding and precision press molding.
< optical element example >
The preforms obtained from the above glass preform examples were annealed to reduce the internal stress of the glass and to fine-tune the refractive index so that the optical properties such as refractive index reached the desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.
< optical Instrument example >
The optical element produced by the above-described optical element embodiments can be used, for example, for imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, by optical design, by forming an optical component or optical assembly using one or more optical elements.
Claims (13)
1. Optical glass, characterized in that its components, expressed in molar percentages, contain: SiO 22:10~30%;B2O3:40~60%;Al2O3:5~20%;La2O3:5~20%;Y2O3: 1 to 15% of (SiO)2+Al2O3)/B2O30.3 to 1.1.
2. An optical glass according to claim 1, characterised in that its composition, expressed in mole percentages, further comprises: gd (Gd)2O3: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or CaO: 0 to 10 percent; and/or SrO: 0 to 10 percent; and/or BaO: 0 to 10 percent; and/or Zr02: 0 to 5 percent; and/or Ta2O5: 0 to 5 percent; and/or Nb2O5: 0 to 5 percent; and/or ZnO: 0 to 10 percent; and/or Rn20: 0 to 10 percent; and/or a clarifying agent: 0 to 1%, of the total amount of Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
3. Optical glass, characterized in that its composition, expressed in mole percentage, is represented by SiO2:10~30%;B2O3:40~60%;Al2O3:5~20%;La2O3:5~20%;Y2O3:1~15%;Gd2O3:0~10%;MgO:0~10%;CaO:0~10%;SrO:0~10%;BaO:0~10%;Zr02:0~5%;Ta2O5:0~5%;Nb2O5:0~5%;ZnO:0~10%;Rn20: 0 to 10 percent; a clarifying agent: 0 to 1% of a component of (SiO)2+Al2O3)/B2O30.3 to 1.1, the Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
4. An optical glass according to any one of claims 1 to 3, wherein the composition, expressed in mole percent, satisfies one or more of the following 5 conditions:
1)(SiO2+Al2O3)/B2O30.4 to 1.0;
2)Al2O3/Ln2O30.3 to 1.5;
3)Ln2O3the/RO is more than 2.0;
4) RO is 0-15%;
5)Ln2O38 to 30%, wherein RO is the total content of MgO, CaO, SrO and BaO, Ln2O3Is La2O3、Y2O3And Gd2O3The total content of (a).
5. An optical glass according to any one of claims 1 to 3, characterised in that its components, expressed in mole percentages, are: SiO 22: 12-25%; and/or B2O3: 42-55%; and/or Al2O3: 7-18%; and/or La2O3: 8-18%; and/or Y2O3: 2-12%; and/or Gd2O3: 0 to 5 percent; and/orMgO: 0-8%; and/or CaO: 0-8%; and/or SrO: 0-8%; and/or BaO: 0-8%; and/or Zr02: 0 to 3 percent; and/or Ta2O5: 0 to 3 percent; and/or Nb2O5: 0 to 3 percent; and/or ZnO: 0 to 5 percent; and/or Rn20: 0 to 5 percent; and/or a clarifying agent: 0 to 0.5%, the Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
6. An optical glass according to any one of claims 1 to 3, wherein the composition, expressed in mole percent, satisfies one or more of the following 5 conditions:
1)(SiO2+Al2O3)/B2O30.5 to 0.8;
2)Al2O3/Ln2O30.4 to 1.2;
3)Ln2O3the/RO is more than 3.0;
4) RO is 0-10%;
5)Ln2O310 to 26% of a total amount of RO, Ln, MgO, CaO, SrO and BaO2O3Is La2O3、Y2O3And Gd2O3The total content of (a).
7. An optical glass according to any one of claims 1 to 3, characterised in that its components, expressed in mole percentages, are: SiO 22: 15-22%; and/or B2O3: 45-52 percent; and/or Al2O3: 8-15%; and/or La2O3: 10-16%; and/or Y2O3: 3-10%; and/or Gd2O3: 0-2%; and/or MgO: 0-6%; and/or CaO: 0-6%; and/or SrO: 0-6%; and/or BaO: 0-6%; and/or Zr02: 0 to 1 percent; and/or Ta2O5: 0 to 1 percent; and/or Nb2O5: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or Rn20: 0-2%; and/or a clarifying agent: 0 to 0.1%, the Rn20 is Li2O、Na2O、K2One or more of O and Sb as clarifier2O3、SnO2SnO and CeO2One or more of (a).
8. An optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in mole percentage, satisfies one or more of the following 4 conditions:
1)Al2O3/Ln2O30.5 to 0.8;
2)Ln2O3the/RO is more than 4.0;
3) RO is 0-8%;
4)Ln2O315 to 22%, wherein RO is the total content of MgO, CaO, SrO and BaO, Ln2O3Is La2O3、Y2O3And Gd2O3The total content of (a).
9. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glassd1.65 to 1.70, preferably a refractive index nd1.66 to 1.69, and more preferably a refractive index ndIs 1.67 to 1.68, and has an Abbe number vd51 to 59, preferably Abbe number vdIs 52 to 58, and the Abbe number v is more preferabledIs 53 to 57.
10. The optical glass according to any one of claims 1 to 3, wherein the optical glass has a water-resistant stability DWIs 2 or more, preferably 1; and/or stability against acid action DAIs 4 or more, preferably 3 or more; and/or Knoop hardness HKIs 650 x 107Pa or more, preferably 670X 107Pa is above; and/or a density p of 3.70g/cm3Hereinafter, it is preferably 3.60g/cm3The following.
11. A glass preform characterized by being made of the optical glass according to any one of claims 1 to 10.
12. An optical element produced from the optical glass according to any one of claims 1 to 10 or the glass preform according to claim 11.
13. An optical device comprising the optical glass according to any one of claims 1 to 10 and/or comprising the optical element according to claim 12.
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CN114907011A (en) * | 2022-06-22 | 2022-08-16 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
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