CN107162404B - Optical glass and optical element - Google Patents
Optical glass and optical element Download PDFInfo
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- CN107162404B CN107162404B CN201610128861.7A CN201610128861A CN107162404B CN 107162404 B CN107162404 B CN 107162404B CN 201610128861 A CN201610128861 A CN 201610128861A CN 107162404 B CN107162404 B CN 107162404B
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- 239000005304 optical glass Substances 0.000 title claims abstract description 56
- 230000003287 optical effect Effects 0.000 title claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 125
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 59
- 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 30
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 29
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 26
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000007704 transition Effects 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 14
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 abstract description 20
- 238000002834 transmittance Methods 0.000 abstract description 18
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 3
- 238000004031 devitrification Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000005499 meniscus Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 230000004075 alteration Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material 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
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 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
- 238000005452 bending Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000005484 gravity 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
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxide Chemical compound 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005303 weighing Methods 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 a refractive index of1.76-1.80, Abbe number 47-51. The optical glass comprises the following components in percentage by weight: SiO 22：0‑3％；B2O3：25‑40％；La2O3：20‑40％；Gd2O3：12‑25％；ZrO2: 6.5 to 15 percent; ZnO: greater than 10% but less than or equal to 20%; ta2O5：0‑5％；Nb2O5：0‑5％；Li2O：0‑10％；(Ta2O5+Nb2O5)/(ZnO+Li2O) less than 0.45; y is2O3: 0 to 10 percent; the glass has a transition temperature Tg of 625 ℃ or lower. According to the invention, through reasonable component proportion, the glass is easy to realize high-refractive-index low-dispersion optical glass which is beneficial to precision mould pressing and has excellent transmittance while realizing the required optical constant.
Description
Technical Field
The present invention relates to an optical glass having a high refractive index and a low dispersion characteristic, and a glass preform and an optical element formed of the optical glass.
Background
In the case of optical glass, the refractive index, Abbe number and transmittance are core optical characteristics. The basic functions of the glass are determined by the refractive index and the Abbe number, the optical glass with the refractive index of 1.76-1.80 and the Abbe number of 47-51 belongs to high-refractive-index low-dispersion optical glass, and the application of the high-performance glass in an optical system can shorten the length of a lens and improve the imaging quality.
In order to meet the requirement of precision compression molding of optical glass, the transition temperature Tg of the optical glass is required. On the premise of realizing the same optical performance, how to realize the low Tg temperature of the glass and ensure excellent transmittance is a research and development target at present. CN102050571A discloses a high refractive index optical glass with a refractive index of 1.77-1.83 and an Abbe number of 44-51, but the Tg temperature is high, and the glass is not suitable for low-cost precision mould pressing. In addition, the glass component contains a large amount of Ta2O5And Ta2O5Belongs to expensive metal oxide, and the use of a large amount of the metal oxide improves the raw material cost of the high-refractive-index low-dispersion optical glass and reduces the economical efficiency of the product. Furthermore, it contains SnO2，SnO2Not only is difficult to melt and is easy to form impurities in the glass, but also influences the inherent quality and the processing performance of the glass, and can improve the coloring degree of the glass and reduce the transmittance. The optical element of the imaging or projection optical system has high requirement on the transmittance of the optical glass, and if the quantity of transmitted light of a lens formed by the high-refraction low-dispersion optical glass is insufficient, the transmitted light flux of the optical system is greatly reduced or suddenly reduced, thereby affecting the imaging quality.
Disclosure of Invention
Hair brushThe technical problem to be solved is to provide a high-refraction low-dispersion optical glass with the refractive index of 1.76-1.80 and the Abbe number of 47-51, and the glass reduces Ta in the glass component2O5The glass has excellent transmittance at the same time of the content.
The present invention also provides a glass preform and an optical element formed of the above optical glass.
The technical scheme adopted by the invention for solving the technical problem is as follows: the optical glass comprises the following components in percentage by weight: SiO 22：0-3％；B2O3：25-40％；La2O3：20-40％；Gd2O3：12-25％；ZrO2: 6.5 to 15 percent; ZnO: greater than 10% but less than or equal to 20%; ta2O5：0-5％；Nb2O5：0-5％；Li2O：0-10％；(Ta2O5+Nb2O5)/(ZnO+Li2O) less than 0.45; y is2O3: 0 to 10 percent; the glass has a transition temperature Tg of 625 ℃ or lower.
Further, the method also comprises the following steps: GeO2：0-10％；Bi2O3：0-10％；Al2O3：0-10％；Na2O：0-10％；K2O：0-10％；CeO2：0-1％；Sb2O3: 0 to 1 percent; and (3) RO: 0-10%, wherein RO is one or more of MgO, CaO, SrO or BaO.
Further, wherein Al2O3: 0-5% and/or Na2O: 0-5% and/or K2O: 0-5% and/or GeO2: 0-5% and/or Bi2O3: 0-5% and/or CeO2: 0-0.5% and/or Sb2O3: 0-0.5% and/or RO: 0 to 5 percent.
Further, wherein Al2O3: 0-1% and/or Na2O: 0-1% and/or K2O: 0-1% and/or GeO2: 0-1% and/or Bi2O3: 0-1% and/or RO: 0 to 1 percent.
Further, wherein (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) 0.30-1.50; la2O3/(La2O3+Gd2O3+Y2O3) 0.38-0.75; ZnO/(B)2O3+SiO2) Is 0.25-0.65.
Further, wherein B2O3: 28.5-35% and/or La2O3: 25-35% and/or Gd2O3: 14-22% and/or ZrO2: 6.5-10% and/or ZnO: 11-16% and/or SiO2: 0-1% and/or Ta2O5: 0-1% and/or Nb2O5: 0-1% and/or Y2O3: 0-7% and/or Li2O：0-5％。
Further, wherein B2O3: 29-32% and/or La2O3: 27-32% and/or Gd2O3: 15-20% and/or ZrO2: 6.5-8.5% and/or ZnO: 11-14.5% and/or SiO2: 0-0.5% and/or Ta2O5: 0-0.5% and/or Nb2O5: 0-0.5% and/or Y2O3: 0.1-5% and/or Li2O：0-1％。
Further, wherein (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.10; and/or La2O3/(La2O3+Gd2O3+Y2O3) 0.45-0.70; and/or ZnO/(B)2O3+SiO2) 0.30-0.55; and/or (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) Is 0.48-1.10.
Further, wherein (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.07; and/or La2O3/(La2O3+Gd2O3+Y2O3) 0.55-0.65; and/or ZnO/(B)2O3+SiO2) 0.30-0.50; and/or (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) Is 0.50-1.0.
Furthermore, the refractive index of the glass is 1.76-1.80; the Abbe number of the glass is 47-51; the density is 5.00g/cm3The following.
The glass preform is made of the optical glass.
The optical element is made of the optical glass.
The invention has the beneficial effects that: not introducing SnO2A component (B) which imparts excellent glass transmittance; by lowering Ta2O5The product cost is optimized; through reasonable component proportion, the glass is easy to realize high-refractivity low-dispersion optical glass which is beneficial to precision mould pressing and has excellent transmittance while realizing the required optical constant, and a glass prefabricated member and an optical element which are formed by the optical glass.
Detailed Description
I, optical glass
The composition of the optical glass of the present invention will be described in detail below, and the content and the total content of each glass component are expressed in% by weight unless otherwise specified, and the ratio of the content to the total content of the glass component is expressed in terms of a weight ratio. In the following description, when a value equal to or less than a predetermined value or a value equal to or greater than the predetermined value is mentioned, the predetermined value is also included.
B2O3Is a glass network forming component and has the functions of improving the glass meltability and reducing the glass transition temperature. In order to achieve the above effects, the present invention introduces more than 25% or more of B2O3However, when the amount of incorporation exceeds 40%, the glass stability is lowered and the refractive index is lowered, so that the high refractive index of the present invention cannot be obtained. Thus, B of the present invention2O3The content of (B) is 25 to 40%, preferably in the range of 28.5 to 35%, more preferably in the range of 29 to 32%.
SiO2Also a glass former, with B2O3The loose chain-like layered networks formed are different, SiO2The three-dimensional network of silicon-oxygen tetrahedrons is formed in the glass, and is very compact and firm. Such network joiningFor loose boron-oxygen triangle [ BO ] in glass3]The network is reinforced to make it compact, thereby increasing the high temperature viscosity of the glass. Meanwhile, the addition of a silicon-oxygen tetrahedral three-dimensional network, and the glass network isolates La2O3、Nb2O5The capability of the cations and the anions for isocrystallization is enhanced, the crystallization threshold value is increased, and the crystallization resistance of the glass is improved. If SiO2The content of (A) is increased unlimitedly, which causes difficulty in dissolution on the one hand, and tends to increase La to maintain a higher refractive index and a low dispersion on the other hand2O3、Gd2O3Equal content of rare earth oxide, SiO2To La2O3The solubility of (A) is low, and the devitrification resistance of the glass is reduced sharply. Therefore, in the present invention, SiO2The content is limited to 0 to 3%, preferably 0 to 1%, and more preferably 0 to 0.5%.
La2O3Are essential components for obtaining the desired optical properties of the present invention. When La2O3When the content of (b) is less than 20%, it is difficult to realize desired optical characteristics; however, when the content exceeds 40%, both devitrification resistance and melting property of the glass deteriorate. Thus, the La of the present invention2O3The content of (B) is 20 to 40%, preferably in the range of 25 to 35%, more preferably in the range of 27 to 32%.
Gd2O3Is an effective component for obtaining high-refractivity optical glass, and is prepared by Gd2O3And La2O3Coexisting, the stability of the glass formed can be improved, but when Gd is used2O3When the content is less than 12%, the above effects are not obvious; if the content exceeds 25%, the devitrification resistance of the glass is lowered and the stability of the formed glass is deteriorated. Thus, Gd of the present invention2O3Is in the range of 12 to 25%, preferably in the range of 14 to 22%, more preferably in the range of 15 to 20%.
The component with high refraction and low dispersion of the invention is preferably also introduced into Y2O3The melting property and devitrification resistance of the glass can be improved and the upper limit temperature of devitrification of the glass can be lowered, but if the content exceeds 10%, the glass is deterioratedThe stability and devitrification resistance are reduced. Thus, Y2O3The content is in the range of 0 to 10%, preferably in the range of 0 to 7%, more preferably in the range of 0.1 to 5%.
La2O3、Gd2O3And Y2O3Among them, La is the component having the greatest effect of increasing the refractive index of the glass and maintaining the stability of the glass2O3. However, if only La is used for the optical glass of the present invention2O3It is difficult to ensure sufficient glass stability. Therefore, La is used in the present invention2O3The component is introduced in relatively large amount, and La is made2O3And Gd2O3Coexistence; or preferably La2O3、Gd2O3And Y2O3Coexistence; more preferably La2O3/(La2O3+Gd2O3+Y2O3) Is in the range of 0.38 to 0.75, and La is more preferable2O3/(La2O3+Gd2O3+Y2O3) In the range of 0.45 to 0.70, more preferably La2O3/(La2O3+Gd2O3+Y2O3) In the range of 0.55 to 0.65, a glass having a high refractive index and a low dispersion and excellent glass stability can be obtained, and the glass is less likely to be colored.
Nb2O5Has excellent effect of improving the refractive index of the glass and reducing the liquid phase temperature, and also has the function of improving the crystallization resistance and the chemical durability of the glass. If the content exceeds 5%, the glass dispersion increases and the optical characteristics of the glass of the present invention cannot be achieved. Thus, Nb2O5The content of (B) is in the range of 0 to 5%, preferably in the range of 0 to 1%, more preferably in the range of 0 to 0.5%.
Ta2O5Has the effect of improving the refractive index, and simultaneously has better effect on maintaining low dispersion of glass than Nb2O5However, in contrast to the other components, Ta2O5The price is very expensive, so the invention reduces the using amount of the catalyst from the aspects of practicability and cost. The inventionTa of2O5The content is 0 to 5%, preferably in the range of 0 to 1%, more preferably 0 to 0.5%.
The addition of a proper amount of ZnO into the glass can improve the chemical stability of the glass and simultaneously can reduce the high-temperature viscosity and the Tg temperature of the glass. However, if the amount of ZnO added is too large, the devitrification resistance of the glass is lowered and the high-temperature viscosity is small, which makes the molding difficult. If the content of ZnO in the glass system is less than 10 percent, the Tg temperature can not meet the design requirement; if the content is more than 20%, the devitrification resistance of the glass is reduced, and the high-temperature viscosity does not meet the design requirement. Therefore, the content of ZnO is limited to more than 10% but less than or equal to 20%, preferably 11 to 16%, more preferably 11 to 14.5%.
In order to obtain glass with low Tg temperature, good stability and easy melting, the inventor finds that when ZnO/(B)2O3+SiO2) In the range of 0.25 to 0.65, preferably ZnO/(B)2O3+SiO2) In the range of 0.30 to 0.55, further preferably ZnO/(B)2O3+SiO2) When the range is 0.30-0.50, the stability and Tg temperature of the glass can be optimally balanced, and a product with better quality can be obtained.
ZrO2The glass belongs to high-refraction oxide, can obviously improve the refractive index of the glass, and simultaneously improves the chemical stability of the glass; in the present invention, ZrO2The glass has the function of improving the abnormal dispersibility of the glass, the abnormal dispersibility of the glass is beneficial to eliminating a secondary spectrum in optical design, if the content of the glass is too low, the effect is not obvious, but if the content of the glass is too much, the crystallization risk of the glass is obviously improved. Therefore, the content thereof is limited to 6.5 to 15%, preferably 6.5 to 10%, more preferably 6.5 to 8.5%.
As an optical glass, the optical transmittance is a very important performance index when (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) When the range of (A) is controlled to 0.30 to 1.50, preferably 0.48 to 1.10, more preferably 0.50 to 1.00, still more preferably 0.50 to 0.70, the preferable range of the refractive index and Abbe number of the present invention can be achieved and the effective suppression of the refractive index and Abbe number can be achievedThe glass is colored and the thermal stability and devitrification resistance of the glass are improved.
Introducing small amount of Al2O3The Al of the present invention can improve the stability and chemical stability of the formed glass, but when the content exceeds 10%, the glass tends to be deteriorated in melting property and to be reduced in devitrification resistance, so that the Al of the present invention2O3The content of (B) is 0 to 10%, preferably 0 to 5%, more preferably 0 to 1%, further preferably not incorporated.
Li2O is added to the glass component and is effective to lower the Tg of the glass. However, low softening point optical glasses are typically melted using platinum or platinum alloy vessels, and during the high temperature melting process, Li in the glass composition+The platinum or platinum alloy vessel is easy to corrode, and the finished glass generates more platinum-containing foreign matters, thereby causing the quality of the glass to be reduced. On the other hand, when such glass is used in a precision press molding process, there is a risk that the surface of the glass member is easily blurred because a mold is generally coated with a release agent containing a carbon element, Li in the glass component easily reacts with the carbon element in the release agent, and a rough opaque film layer is generated on the surface of the glass member. Therefore, the content thereof is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 1%.
Na2O and K2O is an optional component effective for lowering Tg, and if the amount of O is too large, the devitrification temperature is likely to increase and vitrification is difficult, so the content is limited to 0 to 10%, more preferably 0 to 5%, and still more preferably 0 to 1%.
The inventor discovers that Ta is obtained through a large amount of experimental research2O5+Nb2O5The total content of (A) and ZnO + Li2The total content of O has a great influence on the chemical stability and Tg temperature of the glass, when (Ta)2O5+Nb2O5)/(ZnO+Li2O) exceeding 0.45, the Tg of the glass is significantly elevated, which is disadvantageous for precision press-molding, and (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.10, the chemical stability of the present glass is significantly enhanced and the glass density is effectively reduced. In view of this, (Ta) in the glass of the invention2O5+Nb2O5)/(ZnO+Li2O) less than 0.45, preferably (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.10, more preferably (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.07, more preferably (Ta)2O5+Nb2O5)/(ZnO+Li2O) is less than 0.01.
RO (RO is one or more of MgO, CaO, SrO, or BaO) improves the meltability of the glass and adjusts the glass gloss, but when the content thereof exceeds 10%, the devitrification resistance of the glass is lowered, so that the RO content is preferably 0 to 10%, more preferably 0 to 5%, further preferably 0 to 1% in the present invention.
Bi2O3Although the refractive index of the glass can be increased, when it is excessively contained, transmittance on the short wavelength side of the visible light region is lowered, and the glass tends to be colored, so Bi is preferred in the present invention2O3The content is 0 to 10%, more preferably 0 to 5%, still more preferably 0 to 1%, and still more preferably not incorporated.
GeO2The glass forming stability and devitrification resistance can also be effectively improved, but due to GeO2Is a very expensive component, GeO is therefore preferred2The content is 0 to 10%, more preferably 0 to 5%, still more preferably 0 to 1%, and still more preferably not incorporated.
By adding small amounts of Sb2O3、CeO2The component can improve the fining effect of the glass, but when Sb is used2O3When the content exceeds 1%, the glass is at risk of deterioration in devitrification resistance and increase in dispersion, and deterioration of a molding die is promoted by its strong oxidizing action, so that Sb is preferred in the present invention2O3The amount of (B) is 0 to 1%, more preferably 0 to 0.5%, further preferably not added. CeO (CeO)2Function and addition amount ratio of (1) to Sb2The content of O is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably no addition.
F is a component having a large effect of improving the light refractivity and reducing the temperature coefficient of the relative refractive index, but the volatilization thereof in the production process causes a problem of environmental load, and at the same time, a non-uniform portion is formed in the temperature region of the molding operation due to the volatilization thereof from the glass surface, so that it is difficult to be suitable as an optical element.
The properties of the optical glass of the present invention will be described below.
[ optical constants of optical glass ]
The optical glass is high-refractivity low-dispersion glass, and a lens made of the high-refractivity low-dispersion glass is combined with a lens made of the high-refractivity high-dispersion glass in many cases and is used for chromatic aberration correction. The optical glass of the present invention has a glass refractive index nd in the range of 1.76 to 1.80, preferably in the range of 1.76 to 1.79, more preferably in the range of 1.76 to 1.78, further preferably in the range of 1.77 to 1.78, from the viewpoint of imparting optical characteristics suitable for the use thereof; abbe number v of the glass of the inventiondIn the range of 47 to 51, preferably in the range of 48 to 50, more preferably in the range of 49 to 50.
[ coloring of optical glass ]
Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention80/λ5) And (4) showing. Lambda [ alpha ]80Refers to the wavelength, lambda, corresponding to a glass having a transmittance of 80%5The wavelength corresponding to the glass transmittance of 5% is referred to. Wherein λ is80Was measured using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished, measuring the spectral transmittance in the wavelength region from 280nm to 700nm and showing a wavelength of transmittance of 80%. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glassinLight transmitted through the glass and having an intensity I emitted from a planeoutIn the case of light of (1) through (I)out/IinThe quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glasses, λ80A small value of (a) means that the glass itself is colored very little.
Optics of the inventionGlass lambda80Less than or equal to 400nm, preferably lambda80In the range of less than or equal to 395nm, more preferably lambda80In the range of 390nm or less, further preferably λ80In the range of less than or equal to 385nm, still more preferably lambda80Is less than or equal to 380 nm. Lambda [ alpha ]5Less than or equal to 300nm, preferably lambda5In the range of less than or equal to 290nm, more preferably λ5In the range of less than or equal to 285nm, further preferably lambda5Is less than or equal to 280 nm.
[ Density of optical glass ]
The density of the optical glass is the mass per unit volume at a temperature of 20 ℃ in g/cm3And (4) showing.
The density of the glass of the invention is 5.00g/cm3Hereinafter, it is preferably 4.80g/cm3Hereinafter, more preferably 4.70g/cm3Hereinafter, more preferably 4.60g/cm3The following.
[ transition temperature of optical glass ]
The optical glass gradually changes from a solid state to a plastic state in a certain temperature interval. The transition temperature is a temperature corresponding to an intersection point where extensions of straight line portions of a low temperature region and a high temperature region of a glass sample, which is heated from room temperature to a sag temperature, intersect.
The glass of the present invention has a transition temperature Tg of 625 ℃ or lower, preferably 620 ℃ or lower, more preferably 615 ℃ or lower, and still more preferably 610 ℃ or lower.
II, optical preform and optical element
Next, the optical preform and the optical element of the present invention are described.
The optical preform and the optical element of the present invention are each formed of the above-described optical glass of the present invention. The optical prefabricated member of the invention has the characteristics of high refractive index and low dispersion; the optical element of the present invention has high refractive index and low dispersion characteristics, and can provide optical elements such as various lenses and prisms having high optical values at low cost.
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.
The lens can correct chromatic aberration by combining with a lens made of high-refractivity high-dispersion glass, and is suitable as a lens for chromatic aberration correction. Further, the lens is also effective for the compactness of an optical system.
Further, since the prism has a 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 glass examples ]
The present invention is explained by the following examples, but the present invention should not be limited to these examples.
The melting and shaping methods for producing the optical glass may employ techniques well known to those skilled in the art. The preparation method comprises the steps of weighing and mixing glass raw materials (carbonate, nitrate, sulfate, hydroxide, oxide, boric acid and the like) according to the proportion of glass oxide, putting the mixture into a smelting device (such as a platinum crucible), then carrying out appropriate stirring, clarification and homogenization at 1150-1400 ℃, cooling to below 1250 ℃, pouring or leaking into a forming die, and finally carrying out post-treatment such as annealing and processing or directly carrying out compression forming by a precise compression technology.
The characteristics of each glass of the present invention were measured by the following methods, and the measurement results are shown in tables 1 to 9.
(1) Refractive index nd and Abbe number vd
The refractive index and the Abbe number were measured according to the method specified in GB/T7962.1-2010.
(2) Degree of glass coloration (. lamda.)80、λ5)
The spectral transmittance was measured using a glass sample having a thickness of 10. + -. 0.1mm with two optically polished planes opposed to each other, and calculated from the result thereof.
(3) Glass transition temperature (Tg)
The measurement was carried out according to the method specified in GB/T7962.16-2010.
(4) Specific gravity (ρ)
The measurement was carried out according to the method specified in GB/T7962.20-2010.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
[ optical preform examples ]
The optical glass obtained in example 1 in table 1 was cut into a predetermined size, and a release agent was uniformly applied to the surface of the optical glass, and then the optical glass was heated, softened, and pressure-molded to produce preforms of various lenses and prisms 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.
[ optical element examples ]
The preforms obtained from the above optical preform examples were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to 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 optical element may be coated with an antireflection film.
The invention is optical glass with low cost, excellent transmittance, high refraction and low dispersion, the refractive index is 1.76-1.80, the Abbe number is 47-51, and an optical element formed by the glass can meet the requirements of modern novel photoelectric products.
Claims (12)
1. The optical glass is characterized by comprising the following components in percentage by weight: SiO 22：0-3％；B2O3：25-40％；La2O3：20-40％；Gd2O3：12-25％；ZrO2: 6.5 to 15 percent; ZnO: greater than 10% but less than or equal to 20%; ta2O5：0-5％；Nb2O5: 0 to 5 percent; does not contain Li2O；(Ta2O5+Nb2O5)/(ZnO+Li2O) less than 0.45; y is2O3: 0 to 10 percent; the glass has a transition temperature Tg of 625 deg.C or less, (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) 0.4317-1.50.
2. The optical glass of claim 1, further comprising: GeO2：0-10％；Bi2O3：0-10％；Al2O3：0-10％；Na2O：0-10％；K2O：0-10％；CeO2：0-1％；Sb2O3: 0 to 1 percent; and (3) RO: 0-10%, wherein RO is one or more of MgO, CaO, SrO or BaO.
3. An optical glass according to claim 2, wherein Al is present2O3: 0-5% and/or Na2O: 0-5% and/or K2O: 0-5% and/or GeO2: 0-5% and/or Bi2O3: 0-5% and/or CeO2: 0-0.5% and/or Sb2O3: 0-0.5% and/orRO：0-5％。
4. An optical glass according to claim 2, wherein Al is present2O3: 0-1% and/or Na2O: 0-1% and/or K2O: 0-1% and/or GeO2: 0-1% and/or Bi2O3: 0-1% and/or RO: 0 to 1 percent.
5. An optical glass according to claim 1 or 2, wherein La2O3/(La2O3+Gd2O3+Y2O3) 0.38-0.75; ZnO/(B)2O3+SiO2) Is 0.25-0.65.
6. An optical glass according to claim 1 or 2, wherein B is2O3: 28.5-35% and/or La2O3: 25-35% and/or Gd2O3: 14-22% and/or ZrO2: 6.5-10% and/or ZnO: 11-16% and/or SiO2: 0-1% and/or Ta2O5: 0-1% and/or Nb2O5: 0-1% and/or Y2O3：0-7％。
7. An optical glass according to claim 1 or 2, wherein B is2O3: 29-32% and/or La2O3: 27-32% and/or Gd2O3: 15-20% and/or ZrO2: 6.5-8.5% and/or ZnO: 11-14.5% and/or SiO2: 0-0.5% and/or Ta2O5: 0-0.5% and/or Nb2O5: 0-0.5% and/or Y2O3：0.1-5％。
8. An optical glass according to claim 1 or 2, wherein (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.10; and/or La2O3/(La2O3+Gd2O3+Y2O3) 0.45-0.70; and/or ZnO/(B)2O3+SiO2) 0.30-0.55; and/or (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) Is 0.48-1.10.
9. An optical glass according to claim 1 or 2, wherein (Ta)2O5+Nb2O5)/(ZnO+Li2O) less than 0.07; and/or La2O3/(La2O3+Gd2O3+Y2O3) 0.55-0.65; and/or ZnO/(B)2O3+SiO2) 0.30-0.50; and/or (ZrO)2+Y2O3)/(Nb2O5+Gd2O3) Is 0.50-1.0.
10. An optical glass according to claim 1 or 2, characterised in that the glass has a refractive index of 1.76 to 1.80; the Abbe number of the glass is 47-51; the density is 5.00g/cm3The following.
11. Glass preform made of an optical glass according to claims 1 to 10.
12. An optical element made of the optical glass according to claims 1 to 10.
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| JP2018544520A JP6672472B2 (en) | 2016-03-07 | 2016-11-22 | Optical glass and optical element |
| US16/080,845 US10494294B2 (en) | 2016-03-07 | 2016-11-22 | Optical glass and optical element |
| PCT/CN2016/106786 WO2017152656A1 (en) | 2016-03-07 | 2016-11-22 | Optical glass and optical element |
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