CN103708727A - Fluophosphate optical glass - Google Patents

Fluophosphate optical glass Download PDF

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CN103708727A
CN103708727A CN201210371431.XA CN201210371431A CN103708727A CN 103708727 A CN103708727 A CN 103708727A CN 201210371431 A CN201210371431 A CN 201210371431A CN 103708727 A CN103708727 A CN 103708727A
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optical glass
glass
fluorophosphate optical
fluorophosphate
naf
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CN103708727B (en
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孙伟
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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Abstract

The invention provides a fluophosphate optical glass free of precious materials comprising La2O3, Gd2O3, Y2O3 and Yb2O3 and the like. The fluophosphate optical glass comprises 1-10wt% of P2O5, 20-35wt% of AlF3, 0.1-5wt% of NaF, 5-15wt% of MgF2, 10-30wt% of CaF2, 10-30wt% of BaF2, 15-30wt% of SrF2 and 0-5wt% of Al(PO3)3. The refractive index, the Abbe number, the density and the transition temperature of the optical glass are 1.40-1.50, 90-100, below 3.58g/cm<3> and below 430DEG C respectively, and the wavelength lambda80 corresponding to a transmittance of 80% is below 345nm.

Description

Fluorophosphate optical glass
Technical field
The present invention relates to a kind of fluorophosphate optical glass, the fluorophosphate optical glass that particularly relate to a kind of specific refractory power and be 1.40～1.50, Abbe number is 90～100.
Background technology
In recent years, the universal and use fast along with digital camera, pick up camera and camera mobile phone, also develops optical material rapidly towards the direction of high precision int, miniaturization.For meeting above requirement, using non-spherical lens to carry out optical design becomes main flow.With precise compression molding technology low-cost, high yield, on Optical element manufacturing, more and more come into one's own.
Fluorophosphate optical glass is as applying New Glasses Materials more widely, the optical characteristics with low dispersion, low-refraction, in optical system, can eliminate secondary spectrum especial dispersion, improve resolving power, obviously improve optical system picture element, also have lower softening temperature, directly precise compression molding is made senior non-spherical lens simultaneously.It is 1.42～1.47 opticglass that JP1270537 discloses a kind of specific refractory power, wherein contains expensive La 2o 3, Gd 2o 3, Y 2o 3and Yb 2o 3in at least one composition, increased the production cost of glass.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of La that do not contain 2o 3, Gd 2o 3, Y 2o 3and Yb 2o 3etc. the fluorophosphate optical glass of valuable raw material, the specific refractory power of this opticglass is 1.40～1.50, Abbe number is 90～100.
The technical scheme that technical solution problem of the present invention adopts is: fluorophosphate optical glass, does not contain La 2o 3, Gd 2o 3, Y 2o 3and Yb 2o 3component, specific refractory power is 1.40～1.50, and Abbe number is 90～100, and density is 3.58g/cm 3below, transition temperature is below 430 ℃.
Further, its weight percent consists of: P 2o 5: 1～10%, AlF 3: 20～35%, NaF:0.1～5%, MgF 2: 5～15%, CaF 2: 10～30%, BaF 2: 10～30%, SrF 2: 15～30%, Al (PO 3) 3: 0～5%.
Further, wherein: P 2o 5: 4～8%.
Further, wherein: AlF 3: 25～35%, Al (PO 3) 3: 0～2%.
Further, wherein: NaF:0.5～2.5%.
Further, wherein: CaF 2: 10～20%, BaF 2: 10～20%.
Further, wherein: MgF 2: 5～12%, SrF 2: 15～25%.
Fluorophosphate optical glass, its weight percent consists of: P 2o 5: 1～10%, AlF 3: 20～35%, NaF:0.1～5%, MgF 2: 5～15%, CaF 2: 10～30%, BaF 2: 10～30%, SrF 2: 15～30%, Al (PO 3) 3: 0～5%.
Further, wherein: P 2o 5: 4～8%.
Further, wherein: AlF 3: 25～35%.
Further, wherein: Al (PO 3) 3: 0～2%.
Further, wherein: NaF:0.5～2.5%.
Further, wherein: CaF 2: 10～20%.
Further, wherein: BaF 2: 10～20%.
Further, wherein: MgF 2: 5～12%.
Further, wherein: SrF 2: 15～25%.
Further, P 2o 5: 4～8%, AlF 3: 25～35%, NaF:0.5～2.5%, MgF 2: 5～12%, CaF 2: 10～20%, BaF 2: 10～20%, SrF 2: 15～25%.
The gas preform that adopts above-mentioned fluorophosphate optical glass to make.
The optical element that adopts above-mentioned fluorophosphate optical glass to make.
The opticinstrument that adopts above-mentioned fluorophosphate optical glass to make.
The invention has the beneficial effects as follows: fluorophosphate optical glass density of the present invention (ρ) is 3.58g/cm 3below; Specific refractory power (nd) 1.40～1.50; Abbe number (vd) is 90～100; Transition temperature (Tg) is below 430 ℃; Corresponding wavelength X when transmittance reaches 80% 80below 345nm, and not containing La 2o 3, Gd 2o 3, Y 2o 3and Yb 2o 3etc. valuable raw material, reduced production cost.
Embodiment
To describe each component of opticglass of the present invention below, except as otherwise noted, the ratio of each component concentration is to represent by % by weight.
P 2o 5that network generates body, by the P of its introducing 5+, O 2-it is all the principal element that forms glass skeleton.P 2o 5the stability that can keep glass, and can effectively improve the mechanical property of glass.When its content is lower than 1% time, the tendency towards devitrification of glass increases, bad stability; And when its content surpasses 10%, be difficult to obtain the optical property of expection so P 2o 5content be defined as 1～10%, preferred content is 4～8%.
AlF 3be necessary component of the present invention, in glass, introduce Al 3+, F -with the formation of stabilized glass, can effectively reduce specific refractory power and the dispersion of glass, if AlF 3content is too low, can not obtain required optical constant; But content is too high, the devitrification resistance property of glass worsens.So AlF 3content be defined as 20～35%, preferred content is 25～35%.
NaF can reduce the transition temperature of glass effectively, but its too high levels can cause the thermal expansivity of glass to increase, and water tolerance reduces, so the content of NaF is defined as 0.1～5%, preferred content is 0.5～2.5%.
MgF 2can reduce dispersion and the specific refractory power of glass, can improve the chemical stability of glass simultaneously, but its too high levels can make the devitrification resistance property of glass worsen, so MgF 2content be defined as 5～15%, preferred content is 5～12%.
CaF 2in glass, not only can reduce Abbe number and the proportion of glass, and formation that can stabilized glass, if the too low DeGrain of its content; If its too high levels, glass devitrification resistance property worsens, so CaF 2content be 10～30%, be preferably 10～20%.
BaF 2in glass, can effectively regulate specific refractory power and the stabilized glass of glass to form, if content is too low, not reach above effect; Too high levels, not only makes the specific refractory power of glass increase, and the proportion of glass can increase, and chemical stability worsens, so BaF 2content range be 10～30%, be preferably 10～20.
SrF 2devitrification resistance property to raising glass is effective, and can effectively adjust specific refractory power and the proportion of glass, if but its content is too much, and can make the specific refractory power of glass and dispersion become large, be difficult to reach the optical property of anticipation, also can reduce the chemical stability of glass simultaneously.In order better to obtain optical property of the presently claimed invention, SrF 2content be defined as 15～30%, be preferably 15～25%.
Al (PO 3) 3formation that can stabilized glass, but also can improve physical strength and the chemical stability of glass, but its too high levels, the specific refractory power of glass increases, and cannot reach desired optical constant, so Al (PO 3) 3content be defined as 0～5%, be preferably 0～2%, more preferably do not add.
To the performance of accurate die pressing opticglass of the present invention be described below.
Wherein specific refractory power (nd) value is the annealing value of (2 ℃/h)～(6 ℃/h), and specific refractory power and Abbe number are according to < < GB/T 7962.1-1987 colouless optical glass testing method specific refractory power and abbe number > > test.
Transition temperature (Tg) is according to < < GB/T7962.16-1987 colouless optical glass testing method linear expansivity, transition temperature and sag temperature > > test, that is: sample is in certain temperature range, 1 ℃ of the every rising of temperature, on the expansion curve of sample, low-temperature region and the extension of high-temperature area straight line portion are intersected to the corresponding temperature of its intersection point.
Density is tested according to < < GB/T 7962.20-1987 colouless optical glass testing method density measurement method > >.
Glass is made into the sample of 10mm ± 0.1mm thickness, tested glass reaches the wavelength X of 80% correspondence in transmittance 80.
Through test, opticglass provided by the invention has following performance: density (ρ) is 3.58g/cm 3below; Specific refractory power (nd) 1.40～1.50; Abbe number (vd) is 90～100; Transition temperature (Tg) is below 430 ℃; Corresponding wavelength X when transmittance reaches 80% 80below 345nm.
The present invention also provides a kind of optical element, by above-mentioned opticglass, according to method well known to those skilled in the art, is formed.Because described opticglass has low-refraction and lower glass transformation temperature, described optical element also has low-refraction and lower glass transformation temperature, can be applied to the equipment such as digital camera, digital camera, camera cell phone.
In order further to understand technical scheme of the present invention, will the embodiment of opticglass of the present invention be described now.Should be noted that, these embodiment do not limit the scope of the invention.
The opticglass (embodiment 1～30) showing in table 1～table 3 is by weighing according to the ratio of each embodiment shown in table 1～table 3 and hybrid optical common raw material (as oxide compound, fluorochemical) for glass, mixing raw material is placed in platinum crucible, melting in the temperature of 900～1000 ℃, and after fusing, clarification, stirring and homogenizing, obtain not having bubble and do not contain the not homogeneous melten glass of dissolved substance, this melten glass casting mold in mould is also annealed and formed.
The composition of the embodiment of the present invention 1～30 corresponding wavelength X while reaching 80% with specific refractory power (nd), Abbe number (vd), density (ρ), glass transformation temperature (Tg), transmittance 80result in table 1～table 3, represent together.In these tables, the composition of each component represents by % by weight.
Table 1
Figure BDA00002214853800051
Table 2
Table 3
Figure BDA00002214853800061
From above-described embodiment, can find out, fluorophosphate optical glass density of the present invention (ρ) is 3.58g/cm 3below; Specific refractory power (nd) 1.40～1.50; Abbe number (vd) is 90～100; Transition temperature (Tg) is below 430 ℃; Corresponding wavelength X when transmittance reaches 80% 80below 345nm, and not containing La 2o 3, Gd 2o 3, Y 2o 3and Yb 2o 3etc. valuable raw material, reduced production cost.

Claims (20)

1. fluorophosphate optical glass, is characterized in that, does not contain La 2o 3, Gd 2o 3, Y 2o 3and Yb 2o 3component, specific refractory power is 1.40～1.50, and Abbe number is 90～100, and density is 3.58g/cm 3below, transition temperature is below 430 ℃.
2. fluorophosphate optical glass as claimed in claim 1, is characterized in that, its weight percent consists of: P 2o 5: 1～10%, AlF 3: 20～35%, NaF:0.1～5%, MgF 2: 5～15%, CaF 2: 10～30%, BaF 2: 10～30%, SrF 2: 15～30%, Al (PO 3) 3: 0～5%.
3. fluorophosphate optical glass as claimed in claim 2, is characterized in that, wherein: P 2o 5: 4～8%.
4. fluorophosphate optical glass as claimed in claim 2, is characterized in that, wherein: AlF 3: 25～35%, Al (PO 3) 3: 0～2%.
5. fluorophosphate optical glass as claimed in claim 2, is characterized in that, wherein: NaF:0.5～2.5%.
6. fluorophosphate optical glass as claimed in claim 2, is characterized in that, wherein: CaF 2: 10～20%, BaF 2: 10～20%.
7. fluorophosphate optical glass as claimed in claim 2, is characterized in that, wherein: MgF 2: 5～12%, SrF 2: 15～25%.
8. fluorophosphate optical glass, is characterized in that, its weight percent consists of: P 2o 5: 1～10%, AlF 3: 20～35%, NaF:0.1～5%, MgF 2: 5～15%, CaF 2: 10～30%, BaF 2: 10～30%, SrF 2: 15～30%, Al (PO 3) 3: 0～5%.
9. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: P 2o 5: 4～8%.
10. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: AlF 3: 25～35%.
11. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: Al (P0 3) 3: 0～2%.
12. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: NaF:0.5～2.5%.
13. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: CaF 2: 10～20%.
14. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: BaF 2: 10～20%.
15. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: MgF 2: 5～12%.
16. fluorophosphate optical glass as claimed in claim 8, is characterized in that, wherein: SrF 2: 15～25%.
17. fluorophosphate optical glass as claimed in claim 8, is characterized in that P 2o 5: 4～8%, AlF 3: 25～35%, NaF:0.5～2.5%, MgF 2: 5～12%, CaF 2: 10～20%, BaF 2: 10～20%, SrF 2: 15～25%.
18. adopt the gas preform that in claim 1～17, the fluorophosphate optical glass described in arbitrary claim is made.
19. adopt the optical element that in claim 1～17, the fluorophosphate optical glass described in arbitrary claim is made.
20. adopt the opticinstrument that in claim 1～17, the fluorophosphate optical glass described in arbitrary claim is made.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541110A (en) * 2016-03-02 2016-05-04 华东理工大学 Glass material for filling emeralds and preparation method of glass material
CN111995255A (en) * 2020-08-26 2020-11-27 中国科学院上海光学精密机械研究所 Low thermal expansion perfluorinated glass ceramic and preparation method thereof
CN116143408A (en) * 2023-02-13 2023-05-23 中国科学院西安光学精密机械研究所 Low non-linear fluorophosphate ultraviolet window glass

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427784A (en) * 1979-04-24 1984-01-24 Nippon Kogaku K.K. Fluophosphate optical glass
JPH01270537A (en) * 1988-04-20 1989-10-27 Sumita Kogaku Glass Seizosho:Kk Fluorophosphate optical glass
JPH07172864A (en) * 1993-12-14 1995-07-11 Nikon Corp Fluorinated phosphate based low dispersing optical glass
JPH0774083B2 (en) * 1989-08-28 1995-08-09 ホーヤ株式会社 Fluorophosphate glass
CN101164938A (en) * 2006-10-10 2008-04-23 株式会社小原 Optical glass
CN101941798A (en) * 2009-07-10 2011-01-12 湖北新华光信息材料股份有限公司 Optical glass with low refraction and chromatic dispersion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427784A (en) * 1979-04-24 1984-01-24 Nippon Kogaku K.K. Fluophosphate optical glass
JPH01270537A (en) * 1988-04-20 1989-10-27 Sumita Kogaku Glass Seizosho:Kk Fluorophosphate optical glass
JPH0774083B2 (en) * 1989-08-28 1995-08-09 ホーヤ株式会社 Fluorophosphate glass
JPH07172864A (en) * 1993-12-14 1995-07-11 Nikon Corp Fluorinated phosphate based low dispersing optical glass
CN101164938A (en) * 2006-10-10 2008-04-23 株式会社小原 Optical glass
CN101941798A (en) * 2009-07-10 2011-01-12 湖北新华光信息材料股份有限公司 Optical glass with low refraction and chromatic dispersion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541110A (en) * 2016-03-02 2016-05-04 华东理工大学 Glass material for filling emeralds and preparation method of glass material
CN111995255A (en) * 2020-08-26 2020-11-27 中国科学院上海光学精密机械研究所 Low thermal expansion perfluorinated glass ceramic and preparation method thereof
CN111995255B (en) * 2020-08-26 2022-10-11 中国科学院上海光学精密机械研究所 Low thermal expansion perfluorinated glass ceramic and preparation method thereof
CN116143408A (en) * 2023-02-13 2023-05-23 中国科学院西安光学精密机械研究所 Low non-linear fluorophosphate ultraviolet window glass

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