CN104341100B - High-refractive and high-dispersive optical glass, optical element and optical instrument - Google Patents
High-refractive and high-dispersive optical glass, optical element and optical instrument Download PDFInfo
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- CN104341100B CN104341100B CN201310336770.9A CN201310336770A CN104341100B CN 104341100 B CN104341100 B CN 104341100B CN 201310336770 A CN201310336770 A CN 201310336770A CN 104341100 B CN104341100 B CN 104341100B
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- 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
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- 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
-
- 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/08—Doped silica-based glasses containing boron or halide
- C03C2201/10—Doped silica-based glasses containing boron or halide containing boron
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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Abstract
The present invention provides a kind of high-refractive and high-dispersive optical glass that light transmission rate is excellent.High-refractive and high-dispersive optical glass, component include by weight percentage:SiO2:1~10%, B2O3:8~20%, La2O3:35~50%, Y2O3:0.1~5%, Gd2O3:7~20%, ZrO2:0~10%, TiO2:1~9%, Nb2O5:3~12%, ZnO:1~8%.The present invention does not contain the W of easy coloring by rational component proportion6+And Bi2O3, the degree of staining and light transmission rate of glass are excellent, and stability is preferable, have obtained the high-refractive and high-dispersive optical glass that refractive index is 1.93~2.0, Abbe number is 30~35.
Description
Technical field
The present invention relates to a kind of high-refractive and high-dispersive optical glass, more particularly to a kind of refractive index (nd) be 1.93~
2.0, Abbe number (vd) it is 30~35 high-refractive and high-dispersive optical glass, and prefabricated component, the light being made of the optical glass
Learn element and optical instrument.
Background technology
Today of scientific and technological high speed development, the equipment such as digital camera, DV and camera mobile phone are more and more general
And.By taking traditional slr camera as an example, several pieces spherical lenses are just needed inside a camera lens, and by using high-refraction high-dispersion
Optical glass producing at non-spherical lens, can with it is a piece of replace several pieces spherical lenses, significantly reduce the weight of camera lens.Cause
This, demand of the market to high-refractive and high-dispersive optical glass is just more and more big.
CN102161568 disclose a kind of refractive index be 1.945~1.97, the optical glass that Abbe number is 33~36,
Contain a large amount of W in component6+, this makes glass be easy coloring, and Glass optical transmitance deteriorates.CN102459106 discloses one kind
High-refractive and high-dispersive optical glass contains a considerable amount of Bi in component2O3, a large amount of Bi2O3Glass coloration can not only be made,
And the stability of glass can be significantly reduced.
Invention content
Technical problem to be solved by the invention is to provide a kind of high-refractive and high-dispersive optical glass that light transmission rate is excellent.
The technical proposal for solving the technical problem of the invention is:High-refractive and high-dispersive optical glass, component is by weight
Percentage includes:SiO2:1~10%, B2O3:8~20%, La2O3:35~50%, Y2O3:0.1~5%, Gd2O3:7~20%,
ZrO2:0~10%, TiO2:1~9%, Nb2O5:3~12%, ZnO:1~8%.
Further, also contain:Sb2O3:0~1%, R2O:0~3%, wherein one or more of R Li, Na, K,
It is measured by GB/T7962.12-2010 prescriptive procedures, interior transmitance is 80% or more at 10mm thickness samples 400nm.
Further, composition is by weight percentage:SiO2:1~10%, B2O3:8~20%, La2O3:35~50%,
Y2O3:0.1~5%, Gd2O3:7~20%, ZrO2:0~10%, TiO2:1~9%, Nb2O5:3~12%, ZnO:1~8%,
Sb2O3:0~1%, R2O:0~3%, wherein one or more of R Li, Na, K.
Further, wherein:TiO2/(TiO2+ ZnO) it is more than 0.5, Y2O3/(Y2O3+La2O3+Gd2O3) it is less than 0.1.
Further, wherein:SiO2:3~6%.
Further, wherein:B2O3:10~15%.
Further, wherein:La2O3:38~46%.
Further, wherein:Y2O3:1~3%.
Further, wherein:Gd2O3:10~16%.
Further, wherein:ZrO2:4~8%.
Further, wherein:TiO2:5~9%.
Further, wherein:Nb2O5:5~9%.
Further, wherein:ZnO:1~5%.
Further, wherein:TiO2/(TiO2+ ZnO) it is more than 0.7, Y2O3/(Y2O3+La2O3+Gd2O3) it is less than 0.05.
Further, the optical glass refractive index is 1.93~2.0, and Abbe number is 30~35.
Further, the density of the optical glass is measured by GB/T7962.20-2010 prescriptive procedures, is 5.20g/cm3
Below;The coefficient of expansion is measured by GB/T7962.16-2010 prescriptive procedures, is≤72 × 10-7/ DEG C,;Water-fast effect stability DW
It is 1 grade, acidproof effect stability DAIt is 1 grade.
Using gas preform made of above-mentioned high-refractive and high-dispersive optical glass.
Using optical element made of above-mentioned high-refractive and high-dispersive optical glass.
Using optical instrument made of above-mentioned high-refractive and high-dispersive optical glass.
The beneficial effects of the invention are as follows:By rational component proportion, the W of easy coloring is not contained6+And Bi2O3, glass
Degree of staining and light transmission rate are excellent, and stability is preferable, have obtained refractive index (nd) it is 1.93~2.0, Abbe number (vd) it is 30~35
High-refractive and high-dispersive optical glass.
Specific implementation mode
Each component of optical glass of the present invention is described below, unless otherwise indicated, the ratio of each constituent content is
It is indicated with weight %.
B2O3It is that glass network generates oxide body, is the essential component for constituting glass network, especially reflects group of the lanthanides in height
In glass, B2O3It is to obtain the main component of stabilized glass.Work as B2O3When content is less than 8%, the meltdown property of glass degenerates, resistance to
Devitrification behavior is undesirable;Work as B2O3Content is higher than 20%, and design object, therefore, B is not achieved in the refractive index of glass2O3Content limit
It is set to 8~20%, preferably 10~15%.
SiO2And the network generation oxide body of glass is formed, a certain amount of SiO is added2, the high temperature that can increase glass is viscous
Degree, improves the devitrification resistance and chemical stability of glass.When its content is less than 1%, the production technology poor performance of glass;If its
Content is more than 10%, then the refractive index of glass declines, and devitrification resistance property is deteriorated, therefore, SiO2Content range be 1~10%,
Preferably 3~6%.
La2O3It is the active ingredient for improving glass refraction, it is aobvious to the chemical stability and devitrification resistance effect that improve glass
It writes, but when its content is less than 35%, required optical constant is not achieved;If content is higher than 50%, tendency towards devitrification increases instead,
Therefore, La2O3Content be limited to 35~50%, preferably 38~46%.
Y2O3The refractive index and devitrification resistance that glass can be improved can also adjust the optical constant of glass and improve crystallization
Performance, but when its content is more than 5%, devitrification resistance is obviously deteriorated, therefore, Y2O3Content be 0.1~5%, preferably 1~
3%.
Gd2O3The refractive index and chemical stability that glass can be increased, with a certain amount of Gd2O3With La2O3Consolute, Ke Yiyou
Improve the devitrification resistance property of glass in effect ground.But Gd2O3When content is less than 7%, effect unobvious;Work as Gd2O3Content is higher than 20%
When, the devitrification resistance property of glass can instead deteriorated, therefore, Gd2O3Content be limited to 7~20%, preferably 10~16%.
The present inventor is the study found that by rationally adjusting Y2O3、La2O3And Gd2O3Content in glass and proportioning are carrying
While high glass refraction, moreover it is possible to be obviously improved the chemical stability of glass, therefore, Y2O3/(Y2O3+La2O3+Gd2O3) excellent
Choosing is less than 0.1, Y2O3/(Y2O3+La2O3+Gd2O3) more preferably less than 0.05.
ZrO2Viscosity, hardness, elasticity, refractive index and the chemical stability of optical glass can be improved, and glass can be reduced
Coefficient of thermal expansion.Work as ZrO2Content when being more than 10%, crystallization will occur, and reduce the devitrification resistance of glass, because
This, ZrO2Content be 0~10%, preferably 4~8%.
TiO2It can make glass that there is high refractive index, but too high levels can substantially reduce abbe number and increase crystallization and incline
To, or even glass can be made obviously to colour, and therefore, TiO2Content is limited to 1~9%, preferably 5~9%.
Nb2O5It is the high refraction for obtaining the present invention and the necessary component of high dispersion, is also a kind of raising glass
The component of chemical durability.Work as Nb2O5Content be less than 3% when, design requirement is not achieved in optical constant;And when its content is more than
When 12%, the devitrification resistance of glass reduces, therefore, Nb2O5Content be limited to 3~12%, preferably 5~9%.
ZnO can reduce the coefficient of thermal expansion of glass, improve chemical stability, thermal stability and the refractive index of glass, may be used also
To reduce the tendency towards devitrification of glass.When the content of ZnO is more than 8%, the increased devitrification resistance of glass increases;When the content of ZnO is less than 1%
When, the transition temperature of glass increases, and therefore, the content of ZnO is limited to 1~8%, preferably 1~5%.In this glass, TiO2
With the content and proportioning of ZnO, the degree of staining and light transmission rate of glass will be directly influenced, to light transmission rate expected from acquisition and
Degree of staining, preferably TiO2/(TiO2+ ZnO) it is more than 0.5, more preferable TiO2/(TiO2+ ZnO) it is more than 0.7.
R2O (one or more of R Li, Na, K) can improve the stability and melting behaviour of glass, but introduce
The split-phase trend of glass can mostly be aggravated, therefore, content is 0~3%, is preferably added without.
Sb2O3It is used in the present invention as fining agent, content is limited to 0~1%, is preferably added without.
The performance of the optical glass of the present invention is described below:
Density according to by《GB/T7962.20-2010 colouless optical glass test method density measurement methods》Test.
Refractive index and Abbe number according to《GB/T7962.1-2010 colouless optical glass test method refractive index and dispersion system
Number》Test.The high-refractive and high-dispersive optical glass refractive index (nd) for measuring the present invention is 1.93~2.0, Abbe number (vd) is 30
~35.
Thermalexpansioncoefficientα is by the average value that method measuring temperature is 20~120 DEG C as defined in GB/T7962.16-2010.
Transmitance (being indicated below with τ 400nm) is by GB/T7962.12-2010 prescriptive procedures at 10mm thickness samples 400nm
It measures.
Water-fast effect stability DW(powder method) presses the test method of GB/T17129, calculates according to the following formula:
DW=(B-C)/(B-A) * 100
In formula:DWGlass leaches percentage (%)
The quality (g) of B- filters and sample
The quality (g) of sample after C- filters and erosion
A- filter qualities (g)
By the leaching percentage being calculated, D is stablized into the water-fast effect of optical glassWIt is divided into 6 classes see the table below.
Classification | 1 | 2 | 3 | 4 | 5 | 6 |
Leach percentage (DW) | < 0.04 | 0.04-0.10 | 0.10-0.25 | 0.25-0.60 | 0.60-1.10 | > 1.10 |
Acidproof effect stability DA(powder method) presses the test method of GB/T17129, calculates according to the following formula:
DA=(B-C)/(B-A) * 100
In formula:DAGlass leaches percentage (%)
The quality (g) of B- filters and sample
The quality (g) of sample after C- filters and erosion
A- filter qualities (g)
By the leaching percentage being calculated, D is stablized into the acidproof effect of optical glassAIt is divided into 6 classes see the table below:
Classification | 1 | 2 | 3 | 4 | 5 | 6 |
Leach percentage (DA) | < 0.20 | 0.20-0.35 | 0.35-0.65 | 0.65-1.20 | 1.20-2.20 | > 2.20 |
By test, optical glass of the invention has the following performance:Refractive index (nd) is 1.93~2.0, Abbe number
(vd) it is 30~35, density (ρ) is 5.20g/cm3Hereinafter, the coefficient of expansion (α)≤72 × 10-7/ DEG C, τ 400nm be 80% and with
On, water-fast effect stability DW(powder method) is 1 grade, acidproof effect stability DA(powder method) is 1 grade.
The present invention also provides a kind of optical precast product and optical elements, by above-mentioned optical glass according to those skilled in the art
Well known method is formed.Since there is the optical glass high refractive index and high dispersion, the optical element also to have
High refractive index and high dispersion, can be applied to the equipment such as digital camera, digital camera, camera cell phone.
Embodiment
In order to further appreciate that technical scheme of the present invention, the embodiment of optical glass of the present invention will now be described.It should
It is noted that there is no limit the scope of the present invention for these embodiments.
The optical glass (Examples 1 to 3 0) shown in 1~table of table 3 is by according to each embodiment shown in 1~table of table 3
Ratio weigh and hybrid optical glass common raw material (such as oxide, hydroxide, carbonate, nitrate), will mix
Raw material is placed in platinum crucible, is melted in certain temperature, and after fusing, clarification, stirring and homogenizing, is not had
Bubble and homogeneous melt glass without undissolved substance casting mold and anneal this melten glass in mold.
The composition of the embodiment of the present invention 1~30 and refractive index (nd), Abbe number (vd), density (ρ), the coefficient of expansion (α), τ
The result of 400nm indicates in 1~table of table 3 together.In these tables, the composition of each component is indicated with weight %.
Table 1
Table 2
Table 3
As can be seen from the above embodiments, the refractive index (nd) of optical glass of the present invention is 1.93~2.0, Abbe number (vd)
It is 30~35, density (ρ) is 5.20g/cm3Hereinafter, the coefficient of expansion (α)≤72 × 10-7/ DEG C, τ 400nm are 80% or more, resistance to
Water acts on stability DW(powder method) is 1 grade, acidproof effect stability DA(powder method) is 1 grade, suitable for being widely used in digital photograph
In the equipment such as camera, DV and camera mobile phone.
Claims (19)
1. high-refractive and high-dispersive optical glass, it is characterised in that:Its composition includes by weight percentage:SiO2:1~6%, B2O3:
8~20%, La2O3:35~50%, Y2O3:0.1~5%, Gd2O3:10~20%, ZrO2:0~10%, TiO2:1~8.25%,
Nb2O5:3~12%, ZnO:1.69~8%, TiO2/(TiO2+ ZnO) it is more than 0.7, by GB/T7962.12-2010 prescriptive procedures
It measures, interior transmitance is 80% or more at 10mm thickness samples 400nm.
2. high-refractive and high-dispersive optical glass as described in claim 1, it is characterised in that:Also contain:Sb2O3:0~1%,
R2O:0~3%, wherein one or more of R Li, Na, K.
3. high-refractive and high-dispersive optical glass as described in claim 1, it is characterised in that:Its composition is by weight percentage:
SiO2:1~6%, B2O3:8~20%, La2O3:35~50%, Y2O3:0.1~5%, Gd2O3:10~20%, ZrO2:0~
10%, TiO2:1~8.25%, Nb2O5:3~12%, ZnO:1.69~8%, Sb2O3:0~1%, R2O:0~3%, wherein R
For one or more of Li, Na, K, TiO2/(TiO2+ ZnO) it is more than 0.7.
4. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Y2O3/
(Y2O3+La2O3+Gd2O3) it is less than 0.1.
5. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
SiO2:3~6%.
6. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
B2O3:10~15%.
7. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
La2O3:38~46%.
8. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
Y2O3:1~3%.
9. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
Gd2O3:10~16%.
10. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
ZrO2:4~8%.
11. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
TiO2:5~8.25%.
12. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
Nb2O5:5~9%.
13. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Wherein:
ZnO:1.69~5%.
14. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:Y2O3/
(Y2O3+La2O3+Gd2O3) it is less than 0.05.
15. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:The light
It is 1.93~2.0 to learn glass refraction, and Abbe number is 30~35.
16. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that:The light
The density for learning glass is measured by GB/T7962.20-2010 prescriptive procedures, is 5.20g/cm3Below;The coefficient of expansion presses GB/
T7962.16-2010 prescriptive procedures measure, and are≤72 × 10-7/℃;Water-fast effect stability DWIt is 1 grade, acidproof effect stability
DAIt is 1 grade.
17. pre- using glass made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~16
Product.
18. using optics member made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~16
Part.
19. using optics instrument made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~16
Device.
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CN106348586B (en) * | 2016-08-31 | 2019-03-15 | 湖北新华光信息材料有限公司 | A kind of optical glass and preparation method thereof |
CN109250903B (en) * | 2018-08-17 | 2022-02-18 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument having the same |
CN109250902B (en) * | 2018-08-17 | 2022-02-18 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument having the same |
CN111892296B (en) * | 2020-08-03 | 2022-03-08 | 成都光明光电股份有限公司 | Glass composition |
CN115304274A (en) * | 2022-08-26 | 2022-11-08 | 成都光明光电股份有限公司 | High-refraction high-dispersion optical glass |
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CN104341100A (en) | 2015-02-11 |
CN107686237B (en) | 2019-04-30 |
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