CN117023975A - Optical glass - Google Patents
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- CN117023975A CN117023975A CN202310696534.1A CN202310696534A CN117023975A CN 117023975 A CN117023975 A CN 117023975A CN 202310696534 A CN202310696534 A CN 202310696534A CN 117023975 A CN117023975 A CN 117023975A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 84
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 60
- 239000011521 glass Substances 0.000 claims description 129
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 37
- 230000003287 optical effect Effects 0.000 claims description 33
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- 239000008395 clarifying agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 18
- 230000008025 crystallization Effects 0.000 abstract description 17
- 238000013461 design Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 description 18
- 238000002834 transmittance Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- 238000004031 devitrification Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000005499 meniscus Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229910004116 SrO 2 Inorganic materials 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
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000005540 biological transmission Effects 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
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- -1 compound salt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000411 transmission spectrum Methods 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
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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 optical glass, which comprises the following components in percentage by weight: siO (SiO) 2 ：30～40％；B 2 O 3 ：1～10％；ZrO 2 ：0.5～10％；BaO：32～43％；CaO：3～13％；TiO 2 :1 to 10 percent; znO:1 to 10 percent, wherein (BaO+CaO)/(SiO) 2 +ZnO) is 0.8 to 1.6. Through reasonable component design, the optical glass has the expected refractive index and Abbe number and simultaneously has excellent weather resistance and crystallization resistance.
Description
Technical Field
The present invention relates to an optical glass, and more particularly, to an optical glass excellent in weather resistance and crystallization resistance.
Background
In recent years, optical glass with a refractive index of 1.64-1.71 and an Abbe number of 44-50 is widely applied to the design of optical lenses such as security protection and vehicle-mounted optical systems so as to improve the imaging quality of the optical systems. Optical glass applied to the fields of monitoring, vehicle-mounted and the like is required to have excellent weather resistance so as to prolong the service life of the optical glass in severe environments. Chinese patent CN109467312a discloses an optical glass which has better weatherability but the devitrification resistance of the glass is to be improved.
Disclosure of Invention
The invention aims to provide optical glass with excellent weather resistance and crystallization resistance.
The technical scheme adopted for solving the technical problems is as follows:
the optical glass comprises the following components in percentage by weight: siO (SiO) 2 ：30～40％；B 2 O 3 ：1～10％；ZrO 2 ：0.5～10％；BaO：32～43％；CaO：3～13％；TiO 2 :1 to 10 percent; znO:1 to 10 percent, wherein (BaO+CaO)/(SiO) 2 +ZnO) is 0.8 to 1.6.
Further, the optical glass comprises the following components in percentage by weight: al (Al) 2 O 3 :0 to 6 percent; and/or SrO: 0-5%; and/or MgO: 0-5%; and/or Li 2 O: 0-5%; and/or Na 2 O:0 to 6 percent; and/or K 2 O: 0-5%; and/or WO 3 : 0-5%; and/or Nb 2 O 5 : 0-5%; and/or Ln 2 O 3 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
An optical glass, the components of which are represented by weight percentage and are composed of SiO 2 ：30～40％；B 2 O 3 ：1～10％；ZrO 2 ：0.5～10％；BaO：32～43％；CaO：3～13％；TiO 2 ：1～10％；ZnO：1～10％；Al 2 O 3 ：0～6％；SrO：0～5％；MgO：0～5％；Li 2 O：0～5％；Na 2 O：0～6％；K 2 O：0～5％；WO 3 ：0～5％；Nb 2 O 5 ：0～5％；Ln 2 O 3 : 0-5%; clarifying agent: 0 to 1% of a composition wherein (BaO+CaO)/(SiO) 2 +ZnO) of 0.8 to 1.6, ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
Further, the optical glass comprises the following components in percentage by weight: (BaO+CaO)/(SiO) 2 +ZnO) of 0.9 to 1.5, preferably (BaO+CaO)/(SiO) 2 +ZnO) of 1.05 to 1.4, more preferably (BaO+CaO)/(SiO) 2 +ZnO) is 1.1 to 1.35; and/or SiO 2 BaO is 0.7 to 1.2, preferably SiO 2 BaO is 0.75 to 1.1, more preferably SiO 2 BaO is 0.8 to 1.0, further preferably SiO 2 BaO is 0.85-1.0; and/or (ZnO+BaO)/CaO of 2.8 to 10.0, preferably (ZnO+BaO)/CaO of 3.0 to 9.0, more preferably (ZnO+BaO)/CaO of 3.5 to 8.0, still more preferably (ZnO+BaO)/CaO of 4.0 to 6.5; and/or (ZrO) 2 +CaO)/(TiO 2 +ZnO) of 0.3 to 5.0, preferably (ZrO 2 +CaO)/(TiO 2 +ZnO) is 0.7 to 3.0, more preferably (ZrO) 2 +CaO)/(TiO 2 +ZnO) is 0.8 to 2.5, more preferably (ZrO) 2 +CaO)/(TiO 2 +ZnO) is 1.0 to 2.0.
Further, the optical glass comprises the following components in percentage by weight: tiO (titanium dioxide) 2 /(CaO+Al 2 O 3 ) From 0.1 to 1.5, preferably TiO 2 /(CaO+Al 2 O 3 ) From 0.2 to 1.0, more preferably TiO 2 /(CaO+Al 2 O 3 ) From 0.25 to 0.8, tiO being further preferred 2 /(CaO+Al 2 O 3 ) 0.3 to 0.6; and/or Ln 2 O 3 /TiO 2 Is 1.0 or less, preferably Ln 2 O 3 /TiO 2 Is 0.6 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.3 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.1 or less; and/or (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.2 to 10.0, preferably (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.3 to 5.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.5 to 3.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 0.8 to 2.0; and/or Na 2 O/ZnO is 3.0 or less, preferably Na 2 O/ZnO is0.02 to 2.0, more preferably Na 2 O/ZnO is 0.05 to 1.0, more preferably Na 2 0.1 to 0.5 of O/ZnO; and/or (B) 2 O 3 +ZnO+SrO)/BaO is 0.06 to 0.6, preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.1 to 0.5, more preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.15 to 0.4, more preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.15 to 0.3; and/or SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 1.5 to 10.0, preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 2.0 to 7.0, more preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 2.6 to 5.5, further preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 3.0 to 4.5; and/or (Li) 2 O+Na 2 O+K 2 O)/ZrO 2 Is 2.0 or less, preferably (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 1.0 or less, more preferably (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 0.02 to 0.8, more preferably (Li) 2 O+Na 2 O+K 2 O)/ZrO 2 0.1 to 0.5, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
Further, the optical glass comprises the following components in percentage by weight: siO (SiO) 2 :31 to 38%, preferably SiO 2 : 32-36%; and/or Al 2 O 3 :0.1 to 5%, preferably Al 2 O 3 :0.5 to 3 percent; and/or ZrO 2 :1 to 8%, preferably ZrO 2 :2 to 6 percent; and/or BaO: 34-42%, preferably BaO: 36-40%; and/or CaO: 4-12%, preferably CaO: 5-10%; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or TiO 2 :2 to 8%, preferably TiO 2 : 3-7%; and/or ZnO:2 to 7%, preferably ZnO: 3-7%; and/or Na 2 O:0.1 to 4%, preferably Na 2 O:0.5 to 3 percent; and/or B 2 O 3 :2 to 8%, preferably B 2 O 3 :3 to 6 percent; and/or MgO:0 to 3%, preferably MgO:0 to 1 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 1 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 1 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or Nb 2 O 5 :0 to 3%, preferably Nb 2 O 5 :0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
Furthermore, the optical glass does not contain MgO in the components; and/or does not contain SrO; and/or does not contain Li 2 O; and/or does not contain K 2 O; and/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Nb 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Ln 2 O 3 The Ln is 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
Further, the refractive index n of the optical glass d From 1.64 to 1.71, preferably from 1.65 to 1.70, more preferably from 1.66 to 1.685, abbe number v d 44 to 50, preferably 45 to 49, more preferably 46 to 48.5.
Further, the optical glass has a density ρ of 3.90g/cm 3 Hereinafter, it is preferably 3.80g/cm 3 Hereinafter, it is more preferably 3.70g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha 100/300℃ 100X 10 -7 Preferably 9 or less per K8×10 -7 Preferably not more than/K, more preferably 95X 10 -7 and/K or below; and/or stability against water action D W More than 2 types, preferably 1 type; and/or weather resistance CR is 2 or more, preferably 1; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage; and/or transition temperature T g At 680℃or lower, preferably 670℃or lower, more preferably 660℃or lower; and/or the streak degree is C or more, preferably B or more; and/or a viscosity of 55 poise or less, preferably 1 to 45 poise, more preferably 3 to 35 poise at 1400 ℃; and/or lambda 80 Is 400nm or less, preferably lambda 80 Is 390nm or less, more preferably lambda 80 385nm or less; and/or lambda 5 Is 360nm or less, preferably lambda 5 Is 350nm or less, more preferably lambda 5 Is 345nm or less.
And a glass preform made of the optical glass.
The optical element is made of the optical glass or the glass prefabricated member.
An optical instrument comprising the optical glass and/or comprising the optical element.
The beneficial effects of the invention are as follows: through reasonable component design, the optical glass has the expected refractive index and Abbe number and simultaneously has excellent weather resistance and crystallization resistance.
Detailed Description
The embodiments of the optical glass of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the repeated explanation, the optical glass of the present invention is sometimes referred to simply as glass in the following description, although the explanation is omitted appropriately, and the gist of the present invention is not limited thereto.
[ optical glass ]
The ranges of the respective components (ingredients) of the optical glass of the present invention are described below. In the present invention, unless otherwise specified, the content and the total content of each component are all expressed in weight percent (wt%), that is, the content and the total content of each component are expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxide. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the optical glass composition of the present invention is 100% when the oxide, the composite salt, the hydroxide, and the like are melted and decomposed and converted into oxide.
Unless otherwise indicated in a particular context, the numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "and/or" as used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.
< essential Components and optional Components >
SiO 2 Is a skeleton of optical glass, and has the functions of maintaining the chemical stability of glass and improving the devitrification resistance of the glass as a glass network generator. In the invention, the SiO content is more than 30% 2 To obtain the above effect, siO is preferred 2 The content of (C) is 31% or more, more preferably SiO 2 The content of (2) is more than 32%; if SiO is 2 If the content of (2) is more than 40%, the glass will have low melting property, the glass will be difficult to be melted, and the inherent quality problems such as stones will be easily formed, and the glass will have a high transition temperature, and the light transmittance of the glass will be deteriorated due to an excessively high melting temperature. Thus, siO 2 The upper limit of the content of (c) is 40%, preferably 38%, more preferably 36%.
B 2 O 3 The glass can be improved in meltability and devitrification resistance, but when the content is too high, the chemical stability of the glass is lowered and the thermal expansion coefficient is adversely affected. Thus, in the present invention B 2 O 3 The content of (2) is 1 to 10%, preferably 2 to 8%, more preferably 3 to 6%.
Al 2 O 3 Can improve the chemical stability of the glass and improve the mechanical strength and weather resistance of the glass, but when the content is too high, the glass is moltenThe crystallization resistance is deteriorated. Thus, al 2 O 3 The content of (2) is 0 to 6%, preferably 0.1 to 5%, more preferably 0.5 to 3%.
ZrO 2 The hardness, refractive index and chemical stability of the optical glass can be improved, the thermal expansion coefficient of the glass can be reduced, and the high-temperature viscosity can be optimized. When ZrO (ZrO) 2 When the content of (b) is too high, devitrification resistance of the glass decreases, melting difficulty increases, melting temperature increases, and inclusion and light transmittance decrease occur in the glass. Thus, zrO in the present invention 2 The content of (2) is 0.5 to 10%, preferably 1 to 8%, more preferably 2 to 6%.
BaO can increase the refractive index of the glass, improve the thermal expansion coefficient and high-temperature viscosity of the glass, and if the content is too high, the chemical stability of the glass is deteriorated. Therefore, the content of BaO is limited to 32 to 43%, preferably 34 to 42%, more preferably 36 to 40%.
In some embodiments, siO is controlled 2 Ratio SiO between the content of BaO and the content of (B) 2 BaO is in the range of 0.7-1.2, which is beneficial to improving the chemical stability and the streak degree of the glass and improving the high-temperature viscosity of the glass. Therefore, siO is preferred 2 BaO is 0.7 to 1.2, more preferably SiO 2 BaO is 0.75 to 1.1, further preferably SiO 2 BaO is 0.8 to 1.0, and SiO is more preferable 2 BaO is 0.85-1.0.
CaO is helpful to improve the refractive index and hardness of the glass and optimize the abrasion degree of the glass, but if the content of CaO is too high, the crystallization resistance of the glass is reduced. Therefore, the CaO content is 3 to 13%, preferably 4 to 12%, more preferably 5 to 10%.
SrO can adjust the refractive index and abbe number of the glass, but if the content is too large, the chemical stability of the glass is lowered, and the cost of the glass is also rapidly increased. Therefore, the content of SrO is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that SrO is absent.
MgO can reduce the relative partial dispersion of the glass, but when the MgO content is too high, the refractive index of the glass is difficult to meet the design requirement, and the crystallization resistance and the stability of the glass are reduced. Accordingly, the MgO content is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that MgO is not contained.
TiO 2 The glass has the functions of improving the refractive index and dispersion of the glass, and the proper amount of the glass can be more stable and reduce the viscosity of the glass. If TiO 2 When the content of (C) is too high, the crystallization tendency of the glass increases and the transition temperature increases. Thus, in the present invention, tiO 2 The content of (2) is 1 to 10%, preferably 2 to 8%, more preferably 3 to 7%.
In some embodiments, the TiO is controlled 2 Content of (3) and CaO and Al 2 O 3 Total CaO+Al content of (C) 2 O 3 Ratio between TiO 2 /(CaO+Al 2 O 3 ) Within the range of 0.1 to 1.5, the density of the glass is reduced, and the crystallization resistance of the glass is prevented from being deteriorated. Therefore, tiO is preferred 2 /(CaO+Al 2 O 3 ) From 0.1 to 1.5, more preferably TiO 2 /(CaO+Al 2 O 3 ) 0.2 to 1.0. Further, control TiO 2 /(CaO+Al 2 O 3 ) In the range of 0.25 to 0.8, the streak degree of the glass can also be optimized. Therefore, tiO is further preferred 2 /(CaO+Al 2 O 3 ) From 0.25 to 0.8, tiO being more preferred 2 /(CaO+Al 2 O 3 ) 0.3 to 0.6.
ZnO can adjust the refractive index and dispersion of the glass, reduce the transition temperature of the glass, and enable the glass to be smelted at a lower temperature, thereby improving the light transmittance of the glass. If the ZnO content is too high, the high-temperature viscosity value of the glass becomes large, the glass molding difficulty is increased, and the crystallization resistance is deteriorated. Accordingly, the content of ZnO is 1 to 10%, preferably 2 to 7%, more preferably 3 to 7%.
In some embodiments, the combined content of BaO and CaO, bao+cao and SiO, is controlled 2 Sum of ZnO and SiO 2 Ratio between +ZnO BaO+CaO)/(SiO) 2 +ZnO) is in the range of 0.8-1.6, can improve the crystallization resistance of the glass and optimize the weather resistance of the glass. Therefore, (BaO+CaO)/(SiO) is preferable 2 +ZnO) of 0.8 to the whole1.6, more preferably (BaO+CaO)/(SiO) 2 +ZnO) is 0.9 to 1.5. Further, the ratio of (BaO+CaO)/(SiO) is controlled 2 +ZnO) is in the range of 1.05 to 1.4, and the high-temperature viscosity and the thermal expansion coefficient of the glass can be further optimized. Therefore, (BaO+CaO)/(SiO) is more preferable 2 +ZnO) is 1.05 to 1.4, more preferably (BaO+CaO)/(SiO) 2 +ZnO) is 1.1 to 1.35.
In some embodiments, control B 2 O 3 Total content B of ZnO and SrO 2 O 3 The ratio between +ZnO+SrO and BaO content (B 2 O 3 The +ZnO+SrO)/BaO is in the range of 0.06-0.6, which is favorable for reducing the density and the transition temperature of the glass, improving the bubble degree of the glass and optimizing the thermal expansion coefficient. Therefore, (B) is preferable 2 O 3 +ZnO+SrO)/BaO is 0.06 to 0.6, more preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.1 to 0.5, more preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.15 to 0.4, and (B) is more preferable 2 O 3 The +ZnO+SrO)/BaO is 0.15 to 0.3.
In some embodiments, controlling the ratio (ZnO+BaO)/CaO between the sum of ZnO and BaO contents ZnO+BaO and CaO content in the range of 2.8 to 10.0 can improve the weather resistance and bubble degree of the glass and prevent the thermal expansion coefficient from deteriorating. Therefore, (ZnO+BaO)/CaO is preferably 2.8 to 10.0, more preferably (ZnO+BaO)/CaO is 3.0 to 9.0, still more preferably (ZnO+BaO)/CaO is 3.5 to 8.0, still more preferably (ZnO+BaO)/CaO is 4.0 to 6.5.
In some embodiments, the ZrO is controlled 2 And the sum of CaO in ZrO 2 +CaO and TiO 2 Total content of TiO with ZnO 2 Ratio between +ZnO and (ZrO 2 +CaO)/(TiO 2 +ZnO) is in the range of 0.3 to 5.0, and can improve the chemical stability and the bubble degree of the glass. Therefore, (ZrO 2 +CaO)/(TiO 2 +ZnO) is 0.3 to 5.0, more preferably (ZrO) 2 +CaO)/(TiO 2 +ZnO) is 0.7 to 3.0. Further, control (ZrO 2 +CaO)/(TiO 2 +ZnO) is in the range of 0.8 to 2.5, and the high-temperature viscosity and transmittance of the glass can be further optimized. Therefore, it is more preferable that (ZrO 2 +CaO)/(TiO 2 +ZnO) of 0From 8 to 2.5, more preferably (ZrO 2 +CaO)/(TiO 2 +ZnO) is 1.0 to 2.0.
Li 2 O can lower the glass transition temperature, adjust the high temperature viscosity of the glass, improve the meltability of the glass, but is disadvantageous to the chemical stability and cost economy of the glass when the content thereof is high. Thus, li in the present invention 2 The content of O is 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred that Li is not contained 2 O。
In some embodiments, siO is controlled 2 Content of (B) and B 2 O 3 、TiO 2 、Al 2 O 3 、Li 2 Total content of O B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 Ratio between O SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is in the range of 1.5 to 10.0, and can improve the transmittance and the streak degree of the glass and prevent the hardness and the high-temperature viscosity of the glass from deteriorating. Therefore, siO is preferred 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 1.5 to 10.0, more preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 2.0 to 7.0, further preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 2.6 to 5.5, siO is more preferable 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 3.0 to 4.5.
Na 2 O has the effect of improving the glass melting property, and can improve the melting effect of the glass, if Na 2 The content of O is too high, and the chemical stability and weather resistance of the glass are reduced. Thus, na 2 O content is 0 to 6%, preferably Na 2 The content of O is 0.1 to 4%, more preferably Na 2 The content of O is 0.5-3%.
In some embodiments, na is controlled 2 Ratio Na between O content and ZnO content 2 O/ZnO is below 3.0, and can be changedGood friability and crystallization resistance of the glass. Therefore, na is preferred 2 The O/ZnO ratio is 3.0 or less. Further, control Na 2 The O/ZnO is in the range of 0.02-2.0, and the bubble degree of the glass can be further optimized. Therefore, na is more preferable 2 O/ZnO is 0.02 to 2.0, more preferably Na 2 O/ZnO is 0.05 to 1.0, more preferably Na 2 The O/ZnO is 0.1 to 0.5.
K 2 O has an effect of improving the thermal stability and meltability of the glass, but if its content exceeds 5%, the devitrification resistance and chemical stability of the glass are deteriorated. Thus, in the present invention K 2 O content is 0 to 5%, preferably K 2 The content of O is 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that K is absent 2 O。
In some embodiments, li is controlled 2 O、Na 2 O、K 2 Total content of O Li 2 O+Na 2 O+K 2 O and ZrO 2 Ratio between the contents of (Li) 2 O+Na 2 O+K 2 O)/ZrO 2 Below 2.0, it is advantageous to obtain the desired optical constants and optimize the high temperature viscosity and weatherability of the glass. Therefore, it is preferable that (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 2.0 or less, more preferably (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 1.0 or less, more preferably (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 0.02 to 0.8, more preferably (Li) 2 O+Na 2 O+K 2 O)/ZrO 2 0.1 to 0.5.
Nb 2 O 5 The refractive index of the glass can be increased, and the chemical stability and devitrification resistance of the glass can be improved, but if the content thereof is excessively large, the dispersion of the glass increases, it is difficult to obtain a glass of a target optical constant, and at the same time, the cost and density of the glass increase, and the short wave transmittance in the visible light region decreases. Thus, nb in the present invention 2 O 5 The content of (2) is 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred that Nb is not contained 2 O 5 。
WO 3 Can improve the refractive index and mechanical strength of the glass, if WO 3 The content of (2) exceeds 5%, the thermal stability of the glass decreases, and the devitrification resistance decreases. Thus, WO 3 The upper limit of the content of (2) is 5%, preferably 3%, more preferably 1%. In some embodiments, it is further preferred that WO is not included 3 。
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of (a) is a component for improving refractive index and chemical stability of glass by mixing Ln 2 O 3 The content of (2) is controlled to 5% or less, and the glass can be prevented from decreasing in devitrification resistance, preferably Ln 2 O 3 The upper limit of the content range is 3%, more preferably 1%. In some embodiments, it is further preferred that Ln is not present 2 O 3 。
In some embodiments, control Ln 2 O 3 /TiO 2 When the glass viscosity is 1.0 or less, the glass can be prevented from being reduced in weather resistance and chemical stability, and the high-temperature viscosity of the glass can be optimized. Therefore, ln is preferable 2 O 3 /TiO 2 Is 1.0 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.6 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.3 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.1 or less.
In some embodiments, znO and Ln are controlled 2 O 3 In total content of ZnO+Ln 2 O 3 With ZrO 2 Ratio between the contents of (ZnO+Ln) 2 O 3 )/ZrO 2 In the range of 0.2-10.0, the transition temperature of the glass can be reduced, and the chemical stability and crystallization resistance of the glass can be improved. Therefore, (ZnO+Ln) is preferable 2 O 3 )/ZrO 2 Is 0.2 to 10.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.3 to 5.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.5 to 3.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 0.8 to 2.0.
In the invention, 0 to 1 percent of Sb is contained 2 O 3 、SnO、SnO 2 、CeO 2 The one or more components in the glass are used as a clarifying agent, so that the clarifying effect of the glass can be improved, the bubble degree of the glass is improved, the content of the clarifying agent is preferably 0-0.5%, and the content of the clarifying agent is more preferably 0-0.2%. Preferably Sb 2 O 3 As a clarifying agent. When Sb is 2 O 3 If the content exceeds 1%, the glass tends to be degraded in fining property, and the strong oxidation promotes corrosion of platinum or platinum alloy vessels for melting the glass and deterioration of molding dies, so that Sb is preferable in the present invention 2 O 3 The content of (2) is 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.2%. SnO and SnO 2 When the content exceeds 1%, the glass tends to be colored, or when the glass is heated, softened, and subjected to press molding or the like to be reformed, sn becomes a starting point of nucleation and devitrification tends to occur. Thus SnO of the present invention 2 The content of (2) is preferably 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.2%; the content of SnO is preferably 0 to 1%, more preferably 0 to 0.5%, and still more preferably 0 to 0.2%. CeO (CeO) 2 Action and content ratio of (2) and SnO 2 The content thereof is preferably 0 to 1%, more preferably 0 to 0.5%, even more preferably 0 to 0.2%, and still more preferably no CeO is contained 2 。
< component not to be contained >
In the glass of the present invention, V, cr, mn, fe, co, ni, cu, ag and oxides of transition metals such as Mo are colored even when they are contained in small amounts, either alone or in combination, and absorb at a specific wavelength in the visible light range, so that the property of the present invention of improving the visible light transmittance effect is impaired, and therefore, in particular, an optical glass having a wavelength transmittance in the visible light range is preferably practically not contained.
Th, cd, tl, os, be and Se oxides have a tendency to be used in a controlled manner as harmful chemical substances in recent years, and are required to provide environmental protection not only in the glass manufacturing process but also in the processing steps and disposal after production. Therefore, in the case where the influence on the environment is emphasized, it is preferable that they are not substantially contained except for unavoidable mixing. As a result, the optical glass becomes practically free from environmental pollutants. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures against the environment.
In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
The term "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the optical glass of the present invention; however, it is also within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing optical glass that are not intentionally added, and that may be present in small or trace amounts in the final optical glass.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (n) d ) With Abbe number (v) d ) Tested according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n d ) The lower limit of (2) is 1.64, preferably 1.65, more preferably 1.66.
In some embodiments, the refractive index (n d ) The upper limit of (2) is 1.71, preferably 1.70, more preferably 1.685.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) The lower limit of (2) is 44, preferably 45, and more preferably 46.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) The upper limit of (2) is 50, preferably 49, more preferably 48.5.
< Density >
The density (. Rho.) of the optical glass was measured according to the method prescribed in GB/T7962.20-2010.
In some embodiments, the optical glass of the present invention has a density (ρ) of 3.90g/cm 3 Hereinafter, it is preferably 3.80g/cm 3 Hereinafter, it is more preferably 3.70g/cm 3 The following is given.
< coefficient of thermal expansion >
Coefficient of thermal expansion (. Alpha.) of optical glass 100/300℃ ) Data at 100-300℃were tested according to the procedure prescribed in GB/T7962.16-2010.
In some embodiments, the optical glass of the present invention has a coefficient of thermal expansion (α 100/300℃ ) 100X 10 -7 Preferably 98X 10, K or less -7 Preferably not more than/K, more preferably 95X 10 -7 and/K or below.
< stability against Water action >
Stability against Water action of optical glass (D W ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the water resistance stability (D W ) More than 2 kinds, preferably 1 kind.
< weather resistance >
The weather resistance (CR) test method of the optical glass is as follows: the sample is placed in a test box in a saturated steam environment with the relative humidity of 90 percent, and the sample is alternately circulated at the temperature of 40-50 ℃ for 15 cycles every 1 hour. Weather resistance categories were classified according to the amount of turbidity change before and after sample placement, and weather resistance classification conditions are shown in table 1:
table 1.
In some embodiments, the optical glass of the present invention has a weatherability (CR) of 2 or more, preferably 1.
< bubble degree >
The bubble degree of the optical glass was measured according to the method prescribed in GB/T7962.8-2010.
In some embodiments, the optical glass of the present invention has a bubble degree of class A or more, preferably class A 0 Above the stage, more preferably A 00 A stage.
< transition temperature >
Transition temperature (T) of optical glass g ) The test was carried out according to the method prescribed in GB/T7962.16-2010.
In some embodiments, the transition temperature (T g ) The temperature is 680℃or lower, preferably 670℃or lower, and more preferably 660℃or lower.
< crystallization resistance >
The testing method of the crystallization resistance comprises the following steps: cutting sample glass into 20×20×10mm, and placing at temperature T g Preserving heat for 15-30 minutes in a muffle furnace with the temperature of between 200 and 250 ℃, taking out and cooling, and observing whether crystals exist on the surface and the inside of the glass or are opacified. If the glass sample is free of opacification and/or crystals, the glass has excellent crystallization resistance. The test method is used for representing the secondary profiling crystallization resistance of the glass.
< streak degree >
The streak degree of the glass of the present invention was measured according to the method specified in MLL-G-174B. The method is to use a fringe instrument consisting of a point light source and a lens, and compare and examine the fringe with a standard sample from the direction of the easiest to see, and the fringe instrument is divided into 4 grades, namely A, B, C, D grades. The A level is that no stripe is visible under the specified detection condition, the B level is that the stripe is fine and dispersed under the specified detection condition, the C level is that the stripe is slightly parallel under the specified detection condition, and the D level is that the stripe is rough under the specified detection condition.
In some embodiments, the optical glass of the present invention has a degree of streaking of class C or more, preferably class B or more.
< high temperature viscosity >
The high temperature viscosity of the optical glass was measured as follows: the high temperature viscosity of the glass was measured using a THETA Rheotronic II high temperature viscometer using a spin method and the unit of the value was dPaS (poise), with a smaller value indicating a smaller viscosity.
In some embodiments, the optical glass of the present invention has a viscosity of 55 poise or less, preferably 1 to 45 poise, more preferably 3 to 35 poise at 1400 ℃.
< coloring degree >
The glass of the present invention has a coloring degree (lambda) for short-wave transmission spectrum characteristics 80 And lambda (lambda) 5 ) And (3) representing. Lambda (lambda) 80 Refers to the wavelength corresponding to the glass transmittance reaching 80%. Lambda (lambda) 80 Is to measure spectral transmittance in a wavelength range from 280nm to 700nm and to exhibit a wavelength of 80% transmittance using glass having a thickness of 10.+ -. 0.1mm having two opposite planes which are parallel to each other and optically polished. The spectral transmittance or transmittance is the intensity I at right angles to the surface of the glass in Transmits through glass and emits intensity I from a plane out In the case of light passing through I out /I in The indicated amounts, and also the transmittance 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, lambda is in the glass 80 The small value of (2) means that the glass itself is extremely little colored and the light transmittance is high.
In some embodiments, λ of the optical glass of the present invention 80 Is 400nm or less, preferably lambda 80 Is 390nm or less, more preferably lambda 80 Is 385nm or less.
In some embodiments, λ of the optical glass of the present invention 5 Is 360nm or less, preferably lambda 5 Is 350nm or less, more preferably lambda 5 Is 345nm or less.
[ method for producing optical glass ]
The manufacturing method of the optical glass comprises the following steps: the glass of the invention is produced by adopting conventional raw materials and processes, including but not limited to oxide, hydroxide, compound salt (such as carbonate, nitrate, sulfate and the like), boric acid and the like as raw materials, after being proportioned according to a conventional method, the proportioned furnace burden is put into a smelting furnace (such as a platinum or platinum alloy crucible) with the temperature of 1200-1400 ℃ to be smelted, and after clarification and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mould and annealed. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and optical element ]
The optical glass thus produced may be used to produce a glass preform by direct drop molding, grinding, or compression molding such as hot press molding. That is, the glass preform may be produced by directly precision drop molding a molten optical glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from an optical glass, and then performing hot press molding and polishing on the preform. The means for producing the glass preform is not limited to the above-described 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 performing hot press molding, precision press molding, and the like to produce optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by an optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms having high optical value.
Examples of the lens include 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, each of which has a spherical or aspherical lens surface.
[ optical instrument ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, image pickup equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of optical glass >
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 2 to 4 were obtained by using the above-described optical glass manufacturing method. The characteristics of each glass were measured by the test method of the present invention, and the measurement results are shown in tables 2 to 4. In the anti-crystallization property test of tables 2 to 4, according to the above test method, glass was marked as "a" without opacification and without crystal particles on the surface and inside, and glass was marked as "B" without opacification and without crystal particles on the inside but with crystal particles on the surface (glass composition with crystal particles on the surface removed by grinding at the time of secondary press forming of glass, but with no crystal particles on the inside and outside of glass being more preferable, glass composition with 1 to 10 crystal particles on the inside was marked as "C", glass was marked as "D" without opacification and with 10 to 20 crystal particles on the inside, and opacification or dense crystal particles on the inside were marked as "x").
Table 2.
Table 3.
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Table 4.
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< example of glass preform >
The glasses obtained in examples 1 to 20 were subjected to polishing, re-hot press molding, and press molding such as precision press molding to prepare various kinds of lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, and preforms such as prisms.
< example of optical element >
The glass preforms obtained in the above examples were annealed, and the refractive index was fine-tuned while reducing the internal stress of the glass so that the optical characteristics such as refractive index reached the desired values.
Next, each preform was ground and polished to produce 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. The surface of the obtained optical element may be coated with an antireflection film.
< example of optical instrument >
The optical elements produced by the above-described optical element embodiments are useful, for example, in imaging devices, sensors, microscopes, medical technology, digital projection, communications, 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 optical components or optical assemblies using one or more optical elements.
Claims (12)
1. The optical glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：30～40％；B 2 O 3 ：1～10％；ZrO 2 ：0.5～10％；BaO：32～43％；CaO：3～13％；TiO 2 :1 to 10 percent; znO:1 to 10 percent, wherein (BaO+CaO)/(SiO) 2 +ZnO) is 0.8 to 1.6.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: al (Al) 2 O 3 :0 to 6 percent; and/or SrO: 0-5%; and/or MgO: 0-5%; and/or Li 2 O: 0-5%; and/or Na 2 O:0 to 6 percent; and/or K 2 O: 0-5%; and/or WO 3 : 0-5%; and/or Nb 2 O 5 : 0-5%; and/or Ln 2 O 3 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
3. An optical glass, characterized in that the components thereof are represented by weight percent and are composed of SiO 2 ：30～40％；B 2 O 3 ：1～10％；ZrO 2 ：0.5～10％；BaO：32～43％；CaO：3～13％；TiO 2 ：1～10％；ZnO：1～10％；Al 2 O 3 ：0～6％；SrO：0～5％；MgO：0～5％；Li 2 O：0～5％；Na 2 O：0～6％；K 2 O：0～5％；WO 3 ：0～5％；Nb 2 O 5 ：0～5％；Ln 2 O 3 : 0-5%; clarifying agent: 0 to 1% of a composition wherein (BaO+CaO)/(SiO) 2 +ZnO) of 0.8 to 1.6, ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
4. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (BaO+CaO)/(SiO) 2 +ZnO) of 0.9 to 1.5, preferably (BaO+CaO)/(SiO) 2 +ZnO) of 1.05 to 1.4, more preferably (BaO+CaO)/(SiO) 2 +ZnO) is 1.1 to 1.35; and/or SiO 2 BaO is 0.7 to 1.2, preferably SiO 2 BaO is 0.75 to 1.1, more preferably SiO 2 BaO is 0.8 to 1.0, further preferably SiO 2 BaO is 0.85-1.0; and/or (ZnO+BaO)/CaO of 2.8 to 10.0, preferably (ZnO+BaO)/CaO of 3.0 to 9.0, more preferably (ZnO+BaO)/CaO of 3.5 to 8.0, still more preferably (ZnO+BaO)/CaO of 4.0 to 6.5; and/or (ZrO) 2 +CaO)/(TiO 2 +ZnO) of 0.3 to 5.0, preferably (ZrO 2 +CaO)/(TiO 2 +ZnO) is 0.7 to 3.0, more preferably (ZrO) 2 +CaO)/(TiO 2 +ZnO) is 0.8 to 2.5, more preferably (ZrO) 2 +CaO)/(TiO 2 +ZnO) is 1.0 to 2.0.
5. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: tiO (titanium dioxide) 2 /(CaO+Al 2 O 3 ) From 0.1 to 1.5, preferably TiO 2 /(CaO+Al 2 O 3 ) From 0.2 to 1.0, more preferably TiO 2 /(CaO+Al 2 O 3 ) From 0.25 to 0.8, tiO being further preferred 2 /(CaO+Al 2 O 3 ) 0.3 to 0.6; and/or Ln 2 O 3 /TiO 2 Is 1.0 or less, preferably Ln 2 O 3 /TiO 2 Is 0.6 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.3 or less, more preferably Ln 2 O 3 /TiO 2 Is 0.1 or less; and/or (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.2 to 10.0, preferably (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.3 to 5.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 Is 0.5 to 3.0, more preferably (ZnO+Ln) 2 O 3 )/ZrO 2 0.8 to 2.0; and/or Na 2 O/ZnO is 3.0 or less, preferably Na 2 O/ZnO is 0.02-2.0, more preferablySelecting Na 2 O/ZnO is 0.05 to 1.0, more preferably Na 2 0.1 to 0.5 of O/ZnO; and/or (B) 2 O 3 +ZnO+SrO)/BaO is 0.06 to 0.6, preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.1 to 0.5, more preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.15 to 0.4, more preferably (B) 2 O 3 +ZnO+SrO)/BaO is 0.15 to 0.3; and/or SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 1.5 to 10.0, preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 2.0 to 7.0, more preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 2.6 to 5.5, further preferably SiO 2 /(B 2 O 3 +TiO 2 +Al 2 O 3 +Li 2 O) is 3.0 to 4.5; and/or (Li) 2 O+Na 2 O+K 2 O)/ZrO 2 Is 2.0 or less, preferably (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 1.0 or less, more preferably (Li 2 O+Na 2 O+K 2 O)/ZrO 2 Is 0.02 to 0.8, more preferably (Li) 2 O+Na 2 O+K 2 O)/ZrO 2 0.1 to 0.5, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
6. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: siO (SiO) 2 :31 to 38%, preferably SiO 2 : 32-36%; and/or Al 2 O 3 :0.1 to 5%, preferably Al 2 O 3 :0.5 to 3 percent; and/or ZrO 2 :1 to 8%, preferably ZrO 2 :2 to 6 percent; and/or BaO: 34-42%, preferably BaO: 36-40%; and/or CaO: 4-12%, preferably CaO: 5-10%; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or TiO 2 : 2-8%, excellentTiO selection 2 : 3-7%; and/or ZnO: 2-7%, preferably ZnO: 3-7%; and/or Na 2 O:0.1 to 4%, preferably Na 2 O:0.5 to 3 percent; and/or B 2 O 3 :2 to 8%, preferably B 2 O 3 :3 to 6 percent; and/or MgO:0 to 3%, preferably MgO:0 to 1 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 1 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 1 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or Nb 2 O 5 :0 to 3%, preferably Nb 2 O 5 :0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
7. An optical glass according to any one of claims 1 to 3, wherein the composition does not contain MgO; and/or does not contain SrO; and/or does not contain Li 2 O; and/or does not contain K 2 O; and/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Nb 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Ln 2 O 3 The Ln is 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
8. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d From 1.64 to 1.71, preferably from 1.65 to 1.70, more preferably from 1.66 to 1.685, abbe number v d 44 to 50, preferably 45 to 49, more preferably 46 to 48.5.
9. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a density ρ of 3.90g/cm 3 Hereinafter, it is preferably 3.80g/cm 3 Hereinafter, it is more preferably 3.70g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha 100/300℃ 100X 10 -7 Preferably 98X 10, K or less -7 Preferably not more than/K, more preferably 95X 10 -7 and/K or below; and/or stability against water action D W More than 2 types, preferably 1 type; and/or weather resistance CR is 2 or more, preferably 1; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage; and/or transition temperature T g At 680℃or lower, preferably 670℃or lower, more preferably 660℃or lower; and/or the streak degree is C or more, preferably B or more; and/or a viscosity of 55 poise or less, preferably 1 to 45 poise, more preferably 3 to 35 poise at 1400 ℃; and/or lambda 80 Is 400nm or less, preferably lambda 80 Is 390nm or less, more preferably lambda 80 385nm or less; and/or lambda 5 Is 360nm or less, preferably lambda 5 Is 350nm or less, more preferably lambda 5 Is 345nm or less.
10. A glass preform produced by using the optical glass according to any one of claims 1 to 9.
11. An optical element, characterized in that it is made of the optical glass according to any one of claims 1 to 9 or made of the glass preform according to claim 10.
12. An optical instrument comprising the optical glass according to any one of claims 1 to 9 and/or the optical element according to claim 11.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310696534.1A CN117023975A (en) | 2023-06-13 | 2023-06-13 | Optical glass |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310696534.1A CN117023975A (en) | 2023-06-13 | 2023-06-13 | Optical glass |
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| CN117023975A true CN117023975A (en) | 2023-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310696534.1A Pending CN117023975A (en) | 2023-06-13 | 2023-06-13 | Optical glass |
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