CN110316961B - Optical glass, glass preform, optical element and optical instrument - Google Patents
Optical glass, glass preform, optical element and optical instrument Download PDFInfo
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- CN110316961B CN110316961B CN201910660486.4A CN201910660486A CN110316961B CN 110316961 B CN110316961 B CN 110316961B CN 201910660486 A CN201910660486 A CN 201910660486A CN 110316961 B CN110316961 B CN 110316961B
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- 239000005304 optical glass Substances 0.000 title claims abstract description 100
- 239000011521 glass Substances 0.000 title claims description 92
- 230000003287 optical effect Effects 0.000 title claims description 39
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 40
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 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 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000002597 diffusion-weighted imaging Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 19
- 238000013461 design Methods 0.000 abstract description 6
- 238000004031 devitrification Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 230000005499 meniscus Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 206010040925 Skin striae Diseases 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910006735 SnO2SnO Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000013329 compounding 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000009477 glass transition Effects 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
- 238000003384 imaging method 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
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 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
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- -1 platinum ions Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 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
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
-
- 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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- 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
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
-
- 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)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Ceramic Engineering (AREA)
- General Physics & Mathematics (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides an optical glass, which comprises the following components in percentage by weight: SiO 22：35～50％；TiO2：20～38％；Na2O：5～25％；K2O：0～10％；BaO：5～20％；Nb2O5: 0 to 10% of Nb2O5/SiO2Is 0.2 or less. Through reasonable component design and proportion, the optical glass has lower density and excellent chemical stability while meeting the expected refractive index and Abbe number, and meets the application in the photoelectric field.
Description
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.67-1.75 and an Abbe number of 26-33.
Background
Today, with the rapid development of technology, devices such as digital cameras, digital video cameras, and mobile phones capable of taking pictures are becoming more and more popular. Taking a traditional single lens reflex as an example, a plurality of spherical lenses are needed in one lens, and a plurality of spherical lenses can be replaced by one aspheric lens processed by high-refractive-index and high-dispersion optical glass, so that the weight of the lens is greatly reduced. However, it is not sufficient to reduce the weight of the optical instrument by merely reducing the number of glass components, and the miniaturization and weight saving can be more effectively achieved by adjusting the compounding ratio of the optical glass components, reducing the density of the glass, and reducing the weight of the optical glass itself.
CN104876440A discloses an optical glass with a refractive index of 1.7-1.75 and an Abbe number of 32-38, which has a high density and is difficult to satisfy the requirement of light weight of the optical glass. The optical glass can be corroded by various liquids (such as acid, alkali, water and the like) in the environment during the use process, so the resistance of the optical glass to the corrosion, namely the chemical stability of the optical glass is important for the use precision and the service life of instruments.
Disclosure of Invention
The invention aims to provide an optical glass with excellent chemical stability and lower density.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) the optical glass comprises the following components in percentage by weight: SiO 22：35～50％；TiO2：20～38％；Na2O：5～25％；K2O：0～10％；BaO：5～20％；Nb2O5: 0 to 10% of Nb2O5/SiO2Is 0.2 or less.
(2) The optical glass as described in (1), which further comprises, in terms of weight percent: b is2O3: 0 to 10 percent; and/or SrO: 0 to 10 percent; and/or CaO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or Ln2O3: 0-6%; and/or ZrO2: 0 to 5 percent; and/or Li2O: 0 to 5 percent; and/or Al2O3: 0 to 5 percent; and/or ZnO: 0 to 5 percent; and/or Sb2O3: 0 to 1% of Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
(3) An optical glass, the composition of which is expressed by weight percentage and contains SiO2：35～50％；TiO2：20～38％；Nb2O5: 0 to 10% of Nb2O5/SiO2Is 0.2 or less, the refractive index nd of the optical glass is 1.67 to 1.75, and the Abbe number vd26 to 33, and a density rho of 3.2g/cm3The following.
(4) The optical glass according to (3), which comprises the following components in percentage by weight: na (Na)2O：5～25％；K2O：0～10％；BaO：5～20％；B2O3：0～10％；SrO：0～10％；CaO：0～10％；MgO：0～10％；Ln2O3：0～6％；ZrO2：0～5％；Li2O：0～5％；Al2O3：0～5％；ZnO：0～5％；Sb2O3: 0 to 1% of Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
(5) The optical glass as described in any one of (1) to (4), which comprises the following components in percentage by weight: TiO 22/SiO20.45 to 1.0; and/or K2O/BaO is below 0.8; and/or Nb2O5/SiO20.01 to 0.2; and/or Nb2O5/TiO20.01 to 0.35; and/or (ZnO + K)2O+ZrO2+MgO+CaO)/SiO2Is 0.3 or less.
(6) The optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: SiO 22: 37-47%; and/or TiO2: 22-32%; and/or Na2O: 10-22%; and/or K2O: 0.5-8%; and/or BaO: 8-16%; and/or Nb2O5: 0.5-6%; and/or B2O3: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or MgO: 0 to 5 percent; and/or Ln2O3: 0 to 3 percent; and/or ZrO2: 0 to 3 percent; and/or Li2O: 0 to 3 percent; and/or Al2O3: 0 to 3 percent; and/or ZnO: 0 to 3 percent; and/or Sb2O3: 0 to 0.5%, wherein Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
(7) The optical glass as described in any one of (1) to (4), which comprises the following components in percentage by weight: TiO 22/SiO20.5 to 0.85; and/or K2The ratio of O/BaO is 0.05-0.6; and/or Nb2O5/SiO20.02 to 0.15; and/or Nb2O5/TiO20.02 to 0.25; and/or (ZnO + K)2O+ZrO2+MgO+CaO)/SiO2Is 0.2 or less.
(8) The optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: SiO 22: 40-45%; and/or TiO2: 25-30%; and/or Na2O: 12-20%; and/or K2O: 1-6%; and/or BaO: 10-15%; and/or Nb2O5: 1-5%; and/or B2O3: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or Ln2O3: 0 to 1 percent; and/or ZrO2: 0-2%; and/or Li2O: 0-2%; and/or Al2O3: 0 to 1 percent; and/or ZnO: 0 to 1% of Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
(9) The optical glass as described in any one of (1) to (4), which comprises the following components in percentage by weight: TiO 22/SiO20.55 to 0.75; and/or K2The ratio of O/BaO is 0.1-0.5; and/or Nb2O5/SiO20.03 to 0.1; and/or Nb2O5/TiO20.05 to 0.2; and/or (ZnO + K)2O+ZrO2+MgO+CaO)/SiO20.01 to 0.15.
(10) The optical glass according to any one of (1) to (4), wherein the components do not contain Li2O; and/or does not contain ZrO2(ii) a And/or no ZnO; and/or does not contain WO3(ii) a And/or do not contain B2O3。
(11) The optical glass according to any one of (1) to (4) having a refractive index nd of 1.67 to 1.75, preferably 1.68 to 1.74, more preferably 1.70 to 1.73; abbe number vd26 to 33, preferably 27 to 32, and more preferably 28 to 32.
(12) The acid-resistance stability D of the optical glass according to any one of (1) to (4)AIs 2 or more, preferably 1; and/or stability against water action DWIs 2 or more, preferably 1; and/or a density rho of 3.2g/cm3Hereinafter, it is preferably 3.1g/cm3The following; and/or coefficient of thermal expansion alpha-30/70℃Is 100 x 10-7Preferably 98X 10 or less,/K-7A value of less than or equal to K, more preferably 95X 10-7below/K; and/or transition temperature TgIs 620 ℃ or lower, preferably 610 ℃ or lower, and more preferably 600 ℃ or lower.
(13) And a glass preform made of the optical glass according to any one of (1) to (12).
(14) And an optical element produced from the optical glass according to any one of (1) to (12) or the glass preform according to (13).
(15) An optical device produced using the optical glass of any one of (1) to (12) or the optical element of (14).
The invention has the beneficial effects that: through reasonable component design and proportion, the optical glass has lower density and excellent chemical stability while meeting the expected refractive index and Abbe number, and meets the application in the photoelectric field.
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. The optical glass of the present invention may be simply referred to as glass in the following.
[ optical glass ]
The ranges of the respective components of the optical glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to 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 to oxides, the total amount of the oxides is 100%.
Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. 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 a skeleton of an optical glass, and has the functions of maintaining the chemical stability of the glass and improving the devitrification resistance of the glass as a glass network forming body. When SiO is present2When the content is less than 35%, it is difficult toTo achieve the above-mentioned effects, thus SiO2The lower limit of the content of (b) is 35%, preferably the lower limit is 37%, more preferably the lower limit is 40%; when SiO is present2When the content of (3) is more than 50%, the glass-melting property is lowered and the transition temperature is raised, so that SiO2The upper limit of the content of (B) is 50%, preferably 47%, more preferably 45%.
TiO2Has the functions of improving the refractive index and dispersion of the glass, can participate in the formation of glass network, can lead the glass to be more stable and reduce the viscosity of the glass by introducing more than 20 percent of TiO2To obtain the above effects, TiO is preferable2The lower limit of the content of (b) is 22%, more preferably the lower limit is 25%; but with a large introduction of TiO2Since the transmittance of the glass in the short wavelength region in the visible light region is lowered and the tendency of the glass to devitrify increases, TiO in the present invention2The upper limit of the content of (B) is 38%, preferably 32%, more preferably 30%.
In some embodiments of the invention, when TiO is used2/SiO2When the amount is less than 0.45, the meltability of the glass is lowered, the striae are deteriorated, and when TiO is used2/SiO2When the amount exceeds 1.0, the chemical stability and optical transmittance of the glass decrease and the density increases, so that TiO in the present invention2/SiO20.45 to 1.0, preferably TiO2/SiO20.5 to 0.85, preferably TiO2/SiO20.55 to 0.75.
Na2O has the function of improving the meltability of the glass, has obvious effect of improving the melting effect and can also reduce the transformation temperature of the glass, and more than 5 percent of Na is introduced into the invention2O to obtain the above effect, preferably Na2The lower limit of the content of O is 10%, and the more preferable lower limit is 12%; when Na is present2The content of O exceeds 25%, the chemical stability and weather resistance of the glass are lowered, and therefore Na2The upper limit of the content of O is 25%, preferably 22%, more preferably 20%.
K2O has the effect of improving the thermal stability and meltability of the glass, but when the content exceeds 10%, the devitrification resistance of the glass is lowered and the density of the glass is increased, so that the present invention is intended to provide a glass having a high glass strengthIn the invention K2The content of O is 10% or less, preferably K2The content of O is 0.5 to 8%, more preferably 1 to 6%
Li2O can lower the glass transition temperature, but its content is high, which is disadvantageous in acid resistance stability and thermal expansion coefficient of the glass, and in corrosion of a melting vessel (e.g., platinum crucible), therefore, Li2The content of O is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less. In some embodiments, even small amounts of Li are present2O, which also causes the thermal expansion coefficient of the glass to exceed the design requirements and the devitrification resistance to deteriorate, is more preferably not containing Li2O。
MgO can reduce the refractive index and melting temperature of the glass, but when the MgO is added excessively, the refractive index of the glass cannot meet the design requirement, the devitrification resistance and stability of the glass are reduced, and the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.
CaO is useful for adjusting the optical constants of the glass and improving the processability of the glass, but when added in an excessive amount, the optical data of the glass is not satisfactory and the devitrification resistance is deteriorated. Therefore, the content of CaO is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%, and further preferably no CaO is introduced.
The addition of SrO to glass makes it possible to adjust the refractive index and abbe number of the glass, but if the addition amount is too large, the chemical stability of the glass decreases and the cost of the glass rapidly increases. Therefore, the SrO content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.
BaO is an essential component for adjusting the refractive index of the glass, improving the transmittance and strength of the glass in the present invention, and the effect is not significant when the content thereof is less than 5%, preferably the lower limit of the content of BaO is 8%, more preferably the lower limit of the content of BaO is 10%; however, when the content exceeds 20%, the devitrification resistance and chemical stability of the glass are deteriorated. Therefore, the upper limit of the BaO content is 20%, preferably 16%, more preferably 15%.
In some embodiments of the invention, the kit further comprises a second reagent for reducing the concentration of the second reagent in the second reagentLet K2An O/BaO ratio of 0.8 or less is preferable because the hardness of the glass can be increased and the thermal expansion coefficient of the glass can be decreased, and K is preferable2When the O/BaO is within the range of 0.05-0.6, the degree of striae and the anti-devitrification performance of the glass can be optimized, and K is more preferable2The ratio of O/BaO is 0.1 to 0.5.
Nb2O5Is a high-refraction high-dispersion component, can improve the devitrification resistance of the glass, and the Nb is2O5More than 10%, the thermal and chemical stability of the glass is lowered and the optical transmittance is lowered, so that Nb in the present invention is contained2O5The content of (b) is 0 to 10%, preferably 0.5 to 6%, more preferably 1 to 5%.
The inventor of the present invention has found that Nb can be controlled by a large amount of experimental studies2O5/SiO2When the content is 0.2 or less, the chemical stability and devitrification resistance of the glass can be improved and the density of the glass can be reduced, and Nb is preferable2O5/SiO20.01 to 0.2. In some embodiments, Nb is more preferred2O5/SiO2In the range of 0.02 to 0.15, the thermal expansion coefficient of the glass can be optimized, and Nb is further preferred2O5/SiO20.03 to 0.1.
In some embodiments of the invention, the Nb is modified by2O5/TiO2The optical transmittance and glass forming stability of the glass can be improved and the chemical stability of the glass can be optimized by controlling the range of 0.01-0.35, and Nb is preferably selected2O5/TiO20.02 to 0.25, more preferably Nb2O5/TiO20.05 to 0.2.
Al2O3The chemical stability of the glass can be improved to some extent, but the content thereof is too large, and the resistance to devitrification and melting of the glass are lowered, so that the content thereof is 5% or less, preferably 3% or less, and more preferably 1% or less.
B2O3Has an effect of improving the meltability of the glass, but when the content thereof is more than 10%, the chemical stability and devitrification resistance of the glass are lowered. Thus, in the present invention B2O3The upper limit of the content of (B) is 10%, preferably 5%, more preferablyThe upper limit is 3%. In some embodiments, by not introducing B2O3The desired chemical stability can be obtained.
Ln2O3Is a component for improving the refractive index and chemical stability of the glass, is an optional component in the optical glass of the present invention, wherein Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a). By mixing Ln2O3The content of (3) is controlled to 6% or less, whereby the devitrification resistance of the glass can be improved and a desired refractive index and Abbe number can be obtained. Thus, in the optical glass of the present invention, Ln2O3The upper limit of the content range is 6%, preferably 3%, more preferably 1%.
ZnO is added into the glass of the system of the invention, the refractive index and dispersion of the glass can be adjusted, the transition temperature of the glass is reduced, but when the content of ZnO exceeds 5 percent, the devitrification resistance of the glass is reduced, meanwhile, the high-temperature viscosity is smaller, the forming is difficult, and the thermal expansion coefficient and the refractive index temperature coefficient of the glass are increased. Therefore, in the present invention, the ZnO content is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably not contained.
ZrO2Is a component having an increased refractive index, and when the content thereof is large, the devitrification resistance of the glass is lowered, and ZrO in the present invention2The content of (b) is 5% or less, preferably 3% or less, more preferably 2% or less, and further preferably not incorporated.
In some embodiments of the invention, the composition is prepared by reacting (ZnO + K)2O+ZrO2+MgO+CaO)/SiO2When the amount is 0.3 or less, the devitrification resistance and the blister resistance of the glass can be improved and the thermal expansion coefficient of the glass can be reduced, and (ZnO + K) is preferable2O+ZrO2+MgO+CaO)/SiO2Is 0.2 or less, more preferably (ZnO + K)2O+ZrO2+MgO+CaO)/SiO20.01 to 0.15.
By adding 0-1% of Sb2O3、SnO2SnO and CeO2One or more of the components can be used as a fining agent to improve the glassAnd (4) clarifying effect, preferably adding 0-0.5% of clarifying agent. But when Sb is2O3When the content exceeds 1%, the glass tends to have a reduced fining property and the deterioration of the forming mold is promoted by the strong oxidation thereof, so that Sb in the present invention is2O3The amount of (B) is 1% or less, preferably 0.5% or less. SnO2SnO may be added as a fining agent, but when the content exceeds 1%, the glass is colored, or when the glass is heated, softened and press-molded again, Sn tends to become a starting point of nucleation and devitrification occurs, so that the SnO of the present invention2And SnO are contained in an amount of 1% or less, preferably 0.5% or less, and more preferably not contained. CeO (CeO)2Action and addition amount ratio of (B) and SnO2The content is 1% or less, preferably 0.5% or less, and more preferably not contained.
Other components not mentioned above, such as P, can be added as necessary within the range not impairing the characteristics of the glass of the present invention2O5、GeO2、TeO2、Bi2O3、Ta2O5And Ga2O3The upper limit of the content of the above components, which are contained singly or in combination, is preferably 5%, more preferably 3%, still more preferably 1%, and yet still more preferably not contained. In some embodiments of the invention, WO3Since the incorporation of (A) causes deterioration in devitrification resistance and coloring degree of the glass, WO is preferably not contained3。
< 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.
The term "not introduced", "not containing" or "0%" as used herein means that the compound, molecule or element is not intentionally added as a raw material to the optical glass of the present invention; 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 (nd) and Abbe number (. nu.) of optical glassd) The test was carried out according to the method specified in GB/T7962.1-2010.
The refractive index (nd) of the optical glass is 1.67-1.75, preferably 1.68-1.74, and more preferably 1.70-1.73; abbe number (v)d) 26 to 33, preferably 27 to 32, and more preferably 28 to 32.
< 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.
Stability of acid resistance of the optical glass of the present invention (D)A) Is 2 or more, preferably 1.
< 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.
Stability to Water action of the optical glass of the invention (D)W) Is 2 or more, preferably 1.
< Density >
The density (. rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
The optical glass of the present invention has a density (. rho.) of 3.2g/cm3Hereinafter, it is preferably 3.1g/cm3The following.
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of optical glass-30/70℃) And testing data at-30-70 ℃ according to a method specified in GB/T7962.16-2010.
The coefficient of thermal expansion (. alpha.) of the optical glass of the present invention-30/70℃) Is 100 x 10-7Preferably 98X 10 or less,/K-7A value of less than or equal to K, more preferably 95X 10-7and/K is less than or equal to.
< transition temperature >
Transition temperature (T) of optical glassg) The test was carried out according to the method specified in GB/T7962.16-2010.
Transition temperature (T) of the optical glass of the present inventiong) Is 620 ℃ or lower, preferably 610 ℃ or lower, and more preferably 600 ℃ or lower.
< degree of bubbling >
The bubble degree of the optical glass is tested according to the method specified in GB/T7962.8-2010.
The optical glass of the present invention has a bubble degree of B class or more, preferably A class or more, more preferably A class0More than grade.
[ production method ]
The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1200-1350 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. 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 can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass preform may be produced by machining the optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the optical glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing.
It should be noted that the means for producing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
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 preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.
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.
[ optical instruments ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like.
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.
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 in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to 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 obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.
Claims (19)
1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 22：35～50％；TiO2：20～38％；Na2O：5～25％；K2O：0～10％；BaO：5～20％；Nb2O5: 0 to 10% of Nb2O5/SiO2Is 0.188 or less.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: b is2O3: 0 to 10 percent; and/or SrO: 0 to 10 percent; and/or CaO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or Ln2O3: 0-6%; and/or ZrO2: 0 to 5 percent; and/or Li2O: 0 to 5 percent; and/or Al2O3: 0 to 5 percent; and/or ZnO: 0 to 5 percent; and/or Sb2O3: 0 to 1% of Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
3. Optical glass, characterized in that its composition, expressed in weight percent, contains SiO2：35～50％；TiO2：20～38％；Nb2O5: 0 to 10% of Nb2O5/SiO2Is 0.188 or less, the refractive index nd of the optical glass is 1.67 to 1.75, and the Abbe number vd26 to 33, and a density rho of 3.2g/cm3The following.
4. An optical glass according to claim 3, characterised in that its composition, expressed in weight percent, comprises: na (Na)2O：5～25％；K2O：0～10％；BaO：5～20％；B2O3：0～10％；SrO：0～10％；CaO：0～10％；MgO：0～10％；Ln2O3：0～6％；ZrO2：0～5％；Li2O：0～5％；Al2O3：0～5％；ZnO：0～5％；Sb2O3: 0 to 1% of Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
5. An optical glass according to any one of claims 1 to 4, wherein the composition is expressed in weight percent, wherein: TiO 22/SiO20.45 to 1.0; and/or K2O/BaO is below 0.8; and/or Nb2O5/SiO20.01 to 0.188; and/or Nb2O5/TiO20.01 to 0.35; and/or (ZnO + K)2O+ZrO2+MgO+CaO)/SiO2Is 0.3 or less.
6. An optical glass according to any one of claims 1 to 4, comprising, in weight percent: SiO 22: 37-47%; and/or TiO2: 22-32%; and/or Na2O: 10-22%; and/or K2O: 0.5-8%; and/or BaO: 8-16%; and/or Nb2O5: 0.5-6%; and/or B2O3: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or MgO: 0 to 5 percent; and/or Ln2O3: 0 to 3 percent; and/or ZrO2: 0 to 3 percent; and/or Li2O: 0 to 3 percent; and/or Al2O3: 0 to 3 percent; and/or ZnO: 0 to 3 percent; and/or Sb2O3: 0 to 0.5%, wherein Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
7. An optical glass according to any one of claims 1 to 4, wherein the composition is expressed in weight percent, wherein: TiO 22/SiO20.5 to 0.85; and/or K2The ratio of O/BaO is 0.05-0.6; and/or Nb2O5/SiO20.02 to 0.15; and/or Nb2O5/TiO20.02 to 0.25; and/or (ZnO + K)2O+ZrO2+MgO+CaO)/SiO2Is 0.2 or less.
8. An optical glass according to any one of claims 1 to 4, comprising, in weight percent: SiO 22: 40-45%; and/or TiO2: 25-30%; and/or Na2O: 12-20%; and/or K2O: 1-6%; and/or BaO: 10-15%; and/or Nb2O5: 1-5%; and/or B2O3: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or Ln2O3: 0 to 1 percent; and/or ZrO2: 0-2%; and/or Li2O: 0-2%; and/or Al2O3: 0 to 1 percent; and/or ZnO: 0 to 1% of Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
9. An optical glass according to any one of claims 1 to 4, wherein the composition is expressed in weight percent, wherein: TiO 22/SiO20.55 to 0.75; and/or K2The ratio of O/BaO is 0.1-0.5; and/or Nb2O5/SiO20.03 to 0.1; and/or Nb2O5/TiO20.05 to 0.2; and/or (ZnO + K)2O+ZrO2+MgO+CaO)/SiO20.01 to 0.15.
10. An optical glass according to any of claims 1 to 4, wherein the composition does not contain Li2O; and/or does not contain ZrO2(ii) a And/or no ZnO; and/or does not contain WO3(ii) a And/or do not contain B2O3。
11. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index nd of 1.67 to 1.75; abbe number vd26 to 33.
12. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index nd of 1.68 to 1.74; abbe number vdIs 27 to 32.
13. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index nd of 1.70 to 1.73; abbe number vdIs 28 to 32.
14. The optical glass according to any one of claims 1 to 4, wherein the optical glass has an acid-resistance stability DAIs more than 2 types; and/or stability against water action DWIs more than 2 types; and/or a density rho of 3.2g/cm3The following; and/or thermal expansionCoefficient of expansion alpha-30/70℃Is 100 x 10-7below/K; and/or transition temperature TgIs below 620 ℃.
15. The optical glass according to any one of claims 1 to 4, wherein the optical glass has an acid-resistance stability DAIs of type 1; and/or stability against water action DWIs of type 1; and/or a density rho of 3.1g/cm3The following; and/or coefficient of thermal expansion alpha-30/70℃Is 98 x 10-7below/K; and/or transition temperature TgAt a temperature of 610 ℃ or lower.
16. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a coefficient of thermal expansion α-30/70℃Is 95X 10-7below/K; and/or transition temperature TgIs below 600 ℃.
17. A glass preform made of the optical glass according to any one of claims 1 to 16.
18. An optical element produced from the optical glass according to any one of claims 1 to 16 or the glass preform according to claim 17.
19. An optical device comprising the optical glass according to any one of claims 1 to 16 or the optical element according to claim 18.
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| CN111689686B (en) * | 2020-05-12 | 2022-03-08 | 成都光明光电股份有限公司 | Optical glass, glass preform and optical element |
| CN113582537B (en) * | 2021-09-07 | 2022-12-13 | 成都光明光电股份有限公司 | High-refraction high-dispersion optical glass |
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| FR2731423B1 (en) * | 1995-03-07 | 1997-04-30 | Corning France | HIGH REFRACTION GLASSES |
| CN101857357B (en) * | 2010-06-25 | 2012-12-26 | 成都光明光电股份有限公司 | Optical glass and optical element |
| CN108069591A (en) * | 2017-12-13 | 2018-05-25 | 成都光明光电股份有限公司 | Glass composition and chemically toughened glass |
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| JP2000247676A (en) * | 1999-02-24 | 2000-09-12 | Nippon Electric Glass Co Ltd | Optical glass for mold press forming |
| CN101070224A (en) * | 2006-05-12 | 2007-11-14 | 上海新沪玻璃有限公司 | Arsenic-free, lead-free, cadmium free firestone optical glass |
| CN1915875A (en) * | 2006-08-31 | 2007-02-21 | 成都光明光电股份有限公司 | Environmental protective heavy flint optical glass in high refractive index, and high dispersion, and producing method and equipment |
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