WO2010108435A1 - 氟磷酸盐光学玻璃 - Google Patents
氟磷酸盐光学玻璃 Download PDFInfo
- Publication number
- WO2010108435A1 WO2010108435A1 PCT/CN2010/071269 CN2010071269W WO2010108435A1 WO 2010108435 A1 WO2010108435 A1 WO 2010108435A1 CN 2010071269 W CN2010071269 W CN 2010071269W WO 2010108435 A1 WO2010108435 A1 WO 2010108435A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- optical glass
- fluorophosphate
- fluorophosphate optical
- optical
- Prior art date
Links
- 239000005304 optical glass Substances 0.000 title claims abstract description 48
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title claims abstract description 31
- 239000011521 glass Substances 0.000 claims description 68
- 230000003287 optical effect Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 13
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 13
- 230000007704 transition Effects 0.000 claims description 5
- 238000000465 moulding Methods 0.000 abstract description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 abstract 1
- 229910001626 barium chloride Inorganic materials 0.000 abstract 1
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract 1
- 229910001637 strontium fluoride Inorganic materials 0.000 abstract 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 9
- 235000019589 hardness Nutrition 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000004031 devitrification Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000004075 alteration Effects 0.000 description 3
- 239000005303 fluorophosphate glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003856 thermoforming 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
-
- 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
Definitions
- the present invention relates to a fluorophosphate optical glass, and more particularly to a fluorophosphate optical glass having a refractive index (n d ) ranging from 1.45 to 1.52 and an Abbe number (v d ) ranging from 78 to 85. .
- fluorophosphate optical glass not only has low dispersion and low refractive index, but also eliminates the secondary spectral special dispersion in the optical system, improves the resolution, significantly improves the image quality of the optical system, and has low
- the softening point characteristic can be directly molded into a high-grade aspherical lens, which can eliminate the chromatic aberration better, eliminate the spherical aberration and aberration which are difficult to be removed by the spherical optical element, and can replace 2 to 3 spherical lenses to reduce the system volume.
- the melting process of fluorophosphate optical glass is difficult.
- fluorophosphate glass Since the fluorophosphate glass has a large Abbe number and an abnormal partial dispersion property, fluorophosphate glass having an Abbe number of 80 or more has been put into practical use.
- JP-A-2002-234753 discloses a fluorophosphate optical glass having a n d range of 1. 489-1. 510, v d ranging from 79. 2-83. 1, but the mol percentage of MgF 2 in the glass component. The content is 3-6, the glass hardness is small, and the wear is large, which is not conducive to subsequent processing.
- CN1854100A discloses a fluorophosphate optical glass containing a large amount of Li in a glass component. Glass durability is reduced.
- the technical problem to be solved by the present invention is to provide a low refractive fluorophosphate optical glass which is low in refraction and low in dispersion and suitable for molding at a low temperature.
- the technical solution adopted by the present invention to solve the technical problem is: fluorophosphate optical glass, the refractive index of the glass is 1.45-1.52, the Abbe number is 78-85, the transformation temperature is lower than 465 ° C, and the density is lower than 3.8 g. /cm 3 , hardness greater than 360 (10 7 pa).
- composition of the composition is in mol percentage: A1F 3: 18-25%, Al (P0 3 ) 3 : 5-20%, MgF 2 : 7-12%, CaF 2: 15-25%, SrF 2 : 18-25%, BaF 2: 8-20%, Ba (P0 3 ) 2 : 0-8%, YF 3 : 0-3%, BaCl 2 : 0-0.5%.
- composition of the composition is in mol percentage: A1F 3: 18-22%, Al (P0 3 ) 3 : 8-15%, CaF 2 : 17-22%, SrF 2 : 20-25%, BaF 2: 10-17%, Ba (P0 3 ) 2: 1-5%, YF 3 : 0.1-3%
- Fluorophosphate optical glass whose composition is composed of mol percentage: A1F 3: 18-25%, Al (P0 3 ) 3 : 5-20%, MgF 2 : 7-12%, CaF 2: 15-25% , SrF 2 : 18-25%, BaF 2: 8-20%, Ba (P0 3 ) 2: 0-8%, YF 3: 0-3%, BaCl 2: 0-0.5%.
- the glass is discharged at a temperature ranging from 620 to 75 CTC.
- a glass preform made of the fluorophosphate optical glass made of the fluorophosphate optical glass.
- An optical element made of the fluorophosphate optical glass made of the fluorophosphate optical glass.
- the invention has the beneficial effects that the optical glass of the invention has low refractive index and low dispersion, low glass density, high hardness, good processability, low tapping temperature, easy molding, and can effectively prevent streaking from forming.
- A1F 3 is an essential component of the present invention. Al and F are introduced into the glass to stabilize the formation of glass, which can effectively reduce the refractive index and dispersion of the glass. If the content is too low, the desired optical constant range cannot be achieved; the content is too high. , glass resistance to devitrification deteriorated. Therefore, the A1F 3 content is limited to 18-25%, preferably 18-22%.
- Al (P0 3 ) 3 is an essential component of the present invention, and Al, P, and 0 are introduced into the glass to stabilize the glass formation, and the mechanical strength and chemical stability of the glass can also be improved, but if the content is too low, the above cannot be achieved. Effect; The content is too high, the refractive index of the glass increases, and the desired range of glass constant cannot be achieved. Therefore, its content is 5-20%, preferably 8-15%.
- CaF 2 can not only reduce the Abbe number and specific gravity of the glass, but also stabilize the formation of the glass. If the content is too low, the effect is not obvious; if the content is too high, the devitrification resistance of the glass is deteriorated. Therefore, its content ranges from 15 to 25%, preferably from 17 to 22%.
- SrF 2 is effective in adjusting the glass constant and stabilizing the glass formation in the glass. If the content is low, the effect is not remarkable; if the content is too high, the desired optical constant cannot be obtained, and the devitrification resistance is deteriorated. Therefore, its content ranges from 18 to 25%, preferably from 20 to 25%.
- BaF 2 can effectively adjust the refractive index of glass and stabilize glass formation. If the content is too low, the above effect is not achieved. If the content is too high, not only the refractive index of glass will increase, but also the specific gravity of glass will increase. Chemical stability Deterioration. Therefore, its content ranges from 8 to 20%, preferably from 10 to 17%.
- MgF 2 can adjust the glass constant in the glass, improve the hardness and chemical stability of the glass. If the content is too low, the above effect is not achieved; if the content is too high, the glass can be difficult to melt. Therefore, its content ranges from 7 to 12%. Ba (P0 3 ) 2 not only stabilizes the formation of glass in the glass, but also effectively adjusts the glass constant, but the content is too low to achieve the above effects; if the content is too high, the glass is chemically and stably deteriorated. Therefore, its content ranges from 0 to 8%, preferably from 1 to 5%.
- YF 3 can effectively adjust the refractive index of glass in glass, the content is too low, and the above effect is not achieved; if the content is too high, the refractive index of glass exceeds the required range. 1-3% ⁇ Therefore, the content of the range of 0-3%, preferably 0. 1-3%
- BaCl 2 can be introduced as a fining agent, if the content is too high, a C1 Pt melting equipment will cause damage, and therefore the content thereof is limited to the range of 0-0. 5%.
- the method for producing the optical glass of the present invention is:
- the refractive index (n d ) of the optical glass of the present invention is in the range of 1.45-1. 52 , by setting the composition of the glass, in particular, the composition within the above-mentioned preferred range.
- the shell number (V d ) ranges from 78 to 85, the transition temperature (Tg) is below 465 ° C, the density (D) is below 3.8 g/cm 3 , and the glass hardness (H K ) is above 360 (10 7 pa).
- the glass discharge temperature is between 620_750 °C.
- the refractive index (n d ) value is (_2 °C / h) ⁇ ( -6 ° C / h) annealing value, refractive index and dispersion coefficient according to GB/T7962. 1 - 1987 colorless optical glass test method Rate and dispersion coefficient test.
- the transition temperature (Tg) is tested in accordance with GB/T7962. 16-1987 Colorless Optical Glass Test Method for Linear Expansion Coefficient, Transition Temperature and Relaxation Temperature, gp: The sample to be tested is within a certain temperature range, and the temperature is increased by rc. On the expansion curve of the sample to be tested, the linear portion of the low temperature region and the high temperature region are extended to intersect, and the temperature corresponding to the intersection point.
- the density is tested in accordance with GB/T 7962. 20-1987 Colorless Optical Glass Test Method Density Test Method.
- the glass hardness was tested in accordance with GB/T7962. 21-1987 Colorless Optical Glass Test Method Kelvin Hardness.
- the glass boiling temperature test is to make the glass into a sample of 170mm*7mm*7mm, put it into a crystallizing furnace, heat up to 1200 °C, keep it for 4 hours, then take out the sample and cool it to normal temperature, observe the sample with a magnifying glass, according to the glass The crystal condition is measured.
- the optical glass of the present invention can be used as a glass preform for pressure molding, or it can be directly formed by pressure molding of molten glass.
- the manufacturing method and the thermoforming method used as the glass preform are not particularly limited, and a known production method and molding method can be used.
- the glass preform produced by the optical glass of the present invention may be subjected to press working to produce an optical element, or the optical member may be directly subjected to press working on the molten and softened optical glass to produce an optical element.
- the optical element can be used as various lenses, mirrors, prisms, diffraction gratings, and the like, such as lenticular, biconcave, plano-convex, plano-concave, and meniscus lenses.
- the compositions of Examples 1-14 of the optical glass of the present invention are shown in Tables 1 and 2 together with the refractive indices, Abbe numbers, transition temperatures, densities, hardnesses, and furnace temperatures of the glasses, and the composition of each component is in mol. % indicates.
- the optical glass of the embodiment of the present invention has optical constants of the above specific range, that is, the refractive index (n d ) ranges from 1.45 to 1.52, and the Abbe number (v d ) ranges from 78 to 85. , transformation temperature (Tg) below 465 ° C, glass discharge temperature between 620-750 ° C, density (D) 3.8g / cm 3 or less, glass hardness (H K ) 360 (10 7 pa) or more, suitable for Preforms and precision pressure forming for precision pressure forming.
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)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/258,750 US8592331B2 (en) | 2009-03-27 | 2010-03-24 | Fluorophosphate optical glass |
JP2012501122A JP5411347B2 (ja) | 2009-03-27 | 2010-03-24 | フルオロリン酸塩の光学ガラス |
KR1020117024514A KR101251975B1 (ko) | 2009-03-27 | 2010-03-24 | 플루오로인산염 광학 유리 |
EP10755435.4A EP2412684B1 (en) | 2009-03-27 | 2010-03-24 | Fluorophosphate optical glass |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200910301181.0 | 2009-03-27 | ||
CN2009103011810A CN101514079B (zh) | 2009-03-27 | 2009-03-27 | 氟磷酸盐光学玻璃 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010108435A1 true WO2010108435A1 (zh) | 2010-09-30 |
Family
ID=41038714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2010/071269 WO2010108435A1 (zh) | 2009-03-27 | 2010-03-24 | 氟磷酸盐光学玻璃 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8592331B2 (zh) |
EP (1) | EP2412684B1 (zh) |
JP (1) | JP5411347B2 (zh) |
KR (1) | KR101251975B1 (zh) |
CN (1) | CN101514079B (zh) |
WO (1) | WO2010108435A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015209353A (ja) * | 2014-04-25 | 2015-11-24 | 株式会社オハラ | 光学ガラス、光学素子及びプリフォーム |
CN115385572A (zh) * | 2022-09-05 | 2022-11-25 | 湖北新华光信息材料有限公司 | 磷酸盐光学玻璃及其制备方法和光学元件 |
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CN101514079B (zh) | 2009-03-27 | 2012-05-02 | 成都光明光电股份有限公司 | 氟磷酸盐光学玻璃 |
CN102476916B (zh) * | 2010-11-23 | 2013-12-18 | 湖北新华光信息材料有限公司 | 一种中折射率高阿贝数的磷冕光学玻璃 |
CN102211872A (zh) * | 2011-03-23 | 2011-10-12 | 中国科学院上海光学精密机械研究所 | 3μm发光掺稀土离子氟磷酸盐激光玻璃及其制备方法 |
CN102320745B (zh) * | 2011-09-02 | 2013-05-08 | 湖北新华光信息材料有限公司 | 光学玻璃及其制备方法 |
US10393887B2 (en) | 2015-07-19 | 2019-08-27 | Afo Research, Inc. | Fluorine resistant, radiation resistant, and radiation detection glass systems |
CN106904831B (zh) * | 2017-04-01 | 2019-07-09 | 湖北新华光信息材料有限公司 | 光学玻璃及其制备方法和光学元件 |
EP3858796B1 (en) * | 2018-09-28 | 2023-07-12 | CDGM Glass Co. Ltd. | Fluorophosphate optical glass, and optical preform, element and instrument |
CN111484249B (zh) * | 2019-01-25 | 2022-02-25 | 成都光明光电股份有限公司 | 氟磷酸盐玻璃、玻璃预制件、光学元件及具有其的光学仪器 |
CN110156323B (zh) * | 2019-05-31 | 2022-02-11 | 成都光明光电股份有限公司 | 氟磷酸盐玻璃、玻璃预制件、光学元件及具有其的光学仪器 |
CN110156324B (zh) * | 2019-05-31 | 2022-05-24 | 成都光明光电股份有限公司 | 氟磷酸盐玻璃、玻璃预制件、光学元件及具有其的光学仪器 |
CN110156325B (zh) * | 2019-05-31 | 2022-03-11 | 成都光明光电股份有限公司 | 氟磷酸盐玻璃、玻璃预制件、光学元件及具有其的光学仪器 |
JP7535880B2 (ja) * | 2020-05-11 | 2024-08-19 | 株式会社オハラ | 薄板モールドプレス成形用フツリン酸光学ガラス、マルチプレス用フツリン酸光学ガラス、光学素子、プリフォーム及びレンズ |
CN111892298A (zh) * | 2020-09-08 | 2020-11-06 | 成都光明光电股份有限公司 | 光学玻璃、光学预制件及光学元件 |
CN111977974A (zh) * | 2020-09-08 | 2020-11-24 | 成都光明光电股份有限公司 | 光学玻璃、光学预制件、光学元件和光学仪器 |
CN113336439B (zh) * | 2021-07-02 | 2022-07-01 | 湖北新华光信息材料有限公司 | 一种高色散系数光学玻璃及其制备方法和光学元件 |
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CN115385572A (zh) * | 2022-09-05 | 2022-11-25 | 湖北新华光信息材料有限公司 | 磷酸盐光学玻璃及其制备方法和光学元件 |
CN115385572B (zh) * | 2022-09-05 | 2023-07-18 | 湖北新华光信息材料有限公司 | 磷酸盐光学玻璃及其制备方法和光学元件 |
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EP2412684B1 (en) | 2024-05-01 |
EP2412684A4 (en) | 2016-04-06 |
JP5411347B2 (ja) | 2014-02-12 |
CN101514079A (zh) | 2009-08-26 |
EP2412684A1 (en) | 2012-02-01 |
KR20110132454A (ko) | 2011-12-07 |
US20120021891A1 (en) | 2012-01-26 |
CN101514079B (zh) | 2012-05-02 |
US8592331B2 (en) | 2013-11-26 |
JP2012521942A (ja) | 2012-09-20 |
KR101251975B1 (ko) | 2013-04-08 |
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