CN109320064A - Optical glass and the gas preform being made from it, optical element and optical instrument - Google Patents
Optical glass and the gas preform being made from it, optical element and optical instrument Download PDFInfo
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- CN109320064A CN109320064A CN201811128324.8A CN201811128324A CN109320064A CN 109320064 A CN109320064 A CN 109320064A CN 201811128324 A CN201811128324 A CN 201811128324A CN 109320064 A CN109320064 A CN 109320064A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 43
- 230000003287 optical effect Effects 0.000 title claims abstract description 33
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 96
- 230000000694 effects Effects 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 37
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004031 devitrification Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 4
- -1 rare earth ion Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002277 temperature effect Effects 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/004—Re-forming shaped glass by rolling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of optical glass and the gas preforms made of the optical glass, optical element and optical instrument.The composition of optical glass of the invention is indicated by mole %, contains Si4+: 1-10%, B3+: 25-40%, La3+: 20-40%, Gd3+: 0-15%, Y3+: greater than 0 is less than or equal to 10%, Zr4+: 1-10%, Nb5+: 1-12%, Ti4+: 8-25%, wherein (La3++Gd3+)/Y3+For 39-65.Design science of the present invention, formula rationally, have excellent chemical stability, and refractive index is high, and production cost is low.
Description
Technical field
The invention belongs to glass technology fields, and in particular to optical glass and the prefabricated glass made of the optical glass
Part, optical element and optical instrument.
Background technique
The chemical stability of optical glass refers to optical element polished surface in processing, storage and use process to being connect
The resistance to corrosion of the various corrosive mediums of touching.The chemical stability of optical glass is bad, will lead to the anticorrosive of optical element
Ability reduces, and irregular dotted or sheet spot is generated on optical element, to cause the performance and function of optical instrument
It is not up to standard, seriously affect the service life of optical instrument.In the prior art, it is mainly adjusted by alkali metal oxide in glass
Content is to improve its chemical stability.But resulting optical glass has that refractive index is low, high production cost again in this way
The problem of.
Therefore it provides a kind of optical glass, with excellent chemical stability, and refractive index is high, and production cost is low, at
For those skilled in the art's urgent problem to be solved.
Summary of the invention
It is an object of the present invention to: a kind of optical glass is provided, optical glass chemical stabilization in the prior art is solved
The problem of property is bad, refractive index is low, high production cost.
The second object of the present invention is: providing using gas preform made of the light glass.
The third object of the present invention is: providing using optical element made of the light glass.
The fourth object of the present invention is: providing the optical instrument comprising the optical element.
To achieve the above object, The technical solution adopted by the invention is as follows:
Optical glass, composition is indicated by mole %, is contained: Si4+: 1-10%, B3+: 25-40%, La3+: 20-40%,
Gd3+: 0-15%, Y3+: greater than 0 but be less than or equal to 10%, Zr4+: 1-10%, Nb5+: 1-12%, Ti4+: 8-25%, wherein (La3+
+Gd3+)/Y3+For 39-65.
Further, also contain: Zn2+: 0-8%, W6+: 0-10%, R2+: 0-10%, R+: 0-10%, wherein R2+For Ba2+、
Sr2+、Ca2+、Mg2+One of or a variety of, R+For Li+、Na+、K+One of or it is a variety of.
Optical glass, composition are expressed as Si by a mole %4+: 1-10%, B3+: 25-40%, La3+: 20-40%, Gd3+:
0-15%, Y3+: greater than 0 but be less than or equal to 10%, Zr4+: 1-10%, Nb5+: 1-12%, Ti4+: 8-25%, Zn2+: 0-8%, W6 +: 0-10%, R2+: 0-10%, R+: 0-10%, wherein (La3++Gd3+)/Y3+For 39-65, R2+: for Ba2+、Sr2+、Ca2+、Mg2+In
One or more, R+For Li+、Na+、K+One of or it is a variety of.
Further, each component meet one of following 6 kinds of situations or more than one:
1)(La3++Gd3+)/Y3+For 40-60；
2)(Si4++B3+)/Y3+For 36-69；
3)(Nb5++Ti4++W6+)/Y3+For 26-46；
4)Si4+/(La3++Gd3++Y3+) it is 0.02-0.4；
5)(Si4++Zr4+)/(Nb5++Ti4+) it is 0.06-2；
6)La3+/(Si4++Zr4+) it is 1.5-15.
Further, wherein Si4+: 3-9%, and/or B3+: 26-35%, and/or La3+: 25-35%, and/or Gd3+: 0-
10%, and/or Y3+: 0.1-5%, and/or Zr4+: 1-8%, and/or Nb5+: 2-10%, and/or Ti4+: 10-20%, and/or
Zn2+: 0.1-5%, and/or W6+: 0-5%, and/or R2+: 0-5%, and/or R+: 0-5%, wherein R2+: for Ba2+、Sr2+、Ca2+、
Mg2+One of or a variety of, R+For Li+、Na+、K+One of or it is a variety of.
Further, each component meet one of following 6 kinds of situations or more than one:
1)(La3++Gd3+)/Y3+For 42-55；
2)(Si4++B3+)/Y3+For 40-65；
3)(Nb5++Ti4++W6+)/Y3+For 26-40；
4)Si4+/(La3++Gd3++Y3+) it is 0.05-0.3；
5)(Si4++Zr4+)/(Nb5++Ti4+) it is 0.08-1；
6)La3+/(Si4++Zr4+) it is 2-10.
Further, wherein Si4+: 4-8%, and/or B3+: 27-32%, and/or La3+: 26-33%, and/or Gd3+: 1-
8%, and/or Y3+: 0.3-3%, and/or Zr4+: 2-6%, and/or Nb5+: 3-8%, and/or Ti4+: 14-20%, and/or Zn2 +: 1-4%.
Further, each component meet one of following 5 kinds of situations or more than one:
1)(Si4++B3+)/Y3+For 45-58；
2)(Nb5++Ti4++W6+)/Y3+For 28-35；
3)Si4+/(La3++Gd3++Y3+) it is 0.08-0.21；
4)(Si4++Zr4+)/(Nb5++Ti4+) it is 0.1-0.52；
5)La3+/(Si4++Zr4+) it is 2.42-8.
Further, W is not contained6+And/or R2+And/or R+。
Further, the refractive index (nd) of the glass is 1.99-2.01, and Abbe number (vd) is 28-31.
Further, the acidproof effect stability (D of the glassA) it is 2 classes or more, preferably 1 class；The glass it is resistance to
Water acts on stability (DW) it is 2 classes or more, preferably 1 class.
Gas preform is made of above-mentioned optical glass.
Optical element, is made of above-mentioned optical glass or above-mentioned gas preform is made.
Optical instrument includes above-mentioned optical element.
Compared with prior art, the invention has the following advantages:
Design science of the present invention, formula rationally, have excellent chemical stability, and refractive index is high, and production cost is low.
The present invention creatively in the case where reducing the content or not alkali metal containing of alkali metal, passes through the excellent of each component
Change, and to (La3++Gd3+)/Y3+The optimization of ratio, it is excellent to obtain chemical stability, refractive index 1.99-2.01, Abbe
Number is the optical glass of 28-31, meets the high request to Optical Glass Chemical Stability Test and refractive index.
Specific embodiment
In the present specification, in case of no particular description, cationic components content is with the sun for the content of each ingredient
The degree that ion accounts for all cationic total moles indicates, it is total that the anionic component content with the anion accounts for whole anion
Mole degree indicate.In addition, also including this when mentioning specified value or less or specified value or more in the following description
Specified value.
It should be noted that the ioni valence of each ingredient be only for convenience and the typical value that uses, with other ions
Valence is not different.A possibility that ioni valence of each ingredient present in optical glass exists for other than typical value.Such as Si is usual
Exist in glass with the state that ioni valence is 4 valences, therefore in the present specification with " Si4+" as representative, but exist with it
The state of his ioni valence there are a possibility that, while also within protection scope of the present invention.
B in the present invention3+Oxide be glass network former, be the neccessary composition to form glass, have maintain glass
Stability, reduces liquidus temperature and low decentralized effect at meltbility.In the present invention, work as B3+Content is lower than 25%, glass
Crystallization stability it is bad；But work as B3+When content is greater than 40%, the liquidus temperature of glass rises, and chemical stability is deteriorated.Therefore,
Its content range is limited to 25-40%, preferably 26-35%, further preferably 27-32% in the present invention.
Si in the present invention4+Oxide be glass network former, the devitrification resistance energy of glass can be improved in appropriate introduce
And high temperature viscosity；When its content is greater than 10%, the transition temperature of glass can be made to increase, and reduce the meltbility of glass, glass
The chemical stability of glass has the tendency that variation.Therefore, its content range is limited to 1-10%, preferably 3-9% in the present invention, into
One step is preferably 4-8%.
Network modifying oxide of the oxide of rare earth ion as glass in the present invention, is filled primarily with the network in glass
In gap, so that the structure of glass is even closer.Rare earth ion in the present invention is La3+、Gd3+And Y3+。
La in the present invention3+The chemical stability, mechanical strength and refractive index of glass can be improved, and the opposite of glass can be reduced
Partial dispersion, but when its content is more than 40%, the devitrification resistance of glass can will appear obvious deterioration, and content is lower than 20%
When, the chemical stability decline of glass.Therefore, its content range is limited to 20-40%, preferably 25-35% in the present invention, into
One step is preferably 26-33%.
Gd in the present invention3+It can improve the refractive index of glass, and have and improve glass devitrification resistance energy and chemical stability
Effect.But its expensive raw material price, and when its content is more than 15%, glass devitrification resistance reduces and the density of glass is in rising
Trend.Gd in the present invention3+Content range be limited to 0-15%, preferably 0-10%, further preferably 1-8%.
Y in the present invention3+The meltbility of glass can be improved, and improve the devitrification resistance energy and chemical stability of glass.But work as
Its content is more than 10%, and the chemical stability and devitrification resistance of glass can decline.Therefore, Y in the present invention3+The content range upper limit
It is 10%, preferably 8%, more preferably 5%, further preferably 3%, is still more preferably 1%；Y3+Lower limit content is preferred
For greater than 0, more preferably 0.1%, further preferably 0.3%, it is still more preferably 0.5%.
The present inventor is by numerous studies discovery, La3+、Gd3+And Y3+In the presence of common, there is the anti-crystallization for improving glass
The effect of performance and chemical stability.Especially as (La3++Gd3+)/Y3+Value be 39-65 when, glass have excellent chemistry
Stability, preferably 40-60, more preferably as (La3++Gd3+)/Y3+When for 42-55, the acidproof effect stability of glass and water-fast
Effect stability can reach 2 classes or more, preferably 1 class.
The present inventor is the study found that Si4++B3+Total amount and Y3+There are when certain proportion relationship, it help to obtain anti-crystallization
The glass haveing excellent performance, especially as (Si4++B3+)/Y3+Value range when being 36-69, can be in the optical property needed for obtaining
Meanwhile there is excellent devitrification resistance energy, preferably 40-65, further preferably 45-58, it is ensured that glass is being produced and pressed
Crystallization is not easy during type.
The present invention simultaneously it has also been found that, Si4+Total amount with rare earth ion can obtain devitrification resistance energy there are when a proportionate relationship
Excellent glass.Work as Si4+/(La3++Gd3++Y3+) value be greater than 0.4 when, devitrification resistance can deteriorate；When its value is less than 0.02
When, chemical stability is deteriorated.Therefore, Si4+/(La3++Gd3++Y3+) ratio range be limited to 0.02-0.4, preferably 0.05-
0.3, further preferably 0.08-0.21.
In the present invention, Zn2+With the meltbility and chemical stability for improving glass, devitrification resistance energy, and reduce glass
Transition temperature effect.Zn in the present invention2+Content be greater than 8% when, crystallization property deteriorate, dispersion increase, be not able to satisfy
The requirement of refractive index.Zn in the present invention2+Content range be limited to 0-8%, preferably 0.1-5%, further preferably 1-
4%.
In the present invention, Zr4+It can play the role of improving chemical durability of glass.Work as Zr4+Content be 1-10% when,
With suitable refractive index, thermal expansion coefficient, good chemical stability and devitrification resistance energy.When its content is greater than 10%,
The liquidus temperature of glass rises, the decline of glass transmitance；When its content is less than 1%, devitrification resistance can deteriorate, and not be able to satisfy folding
Penetrate the requirement of rate.Zr in the present invention4+Content range be limited to 1-10%, preferably 1-8%, further preferably 2-6%.
The present inventor has found through numerous studies, Si4+、Zr4+Total amount and La3+There are when certain proportion relationship, can obviously mention
Rise the chemical stability of glass.Work as La3+/(Si4++Zr4+) value when being lower than 1.5, the chemical stability of glass is deteriorated；When its value
When higher than 15, devitrification resistance can deteriorate, and not be able to satisfy the requirement of refractive index.In the present invention, La3+/(Si4++Zr4+) value it is preferred
For 2-10, more preferably 2.42-8.
Nb in the present invention5+Have the function of improving glass refraction, increase dispersion, while also having raising glass chemistry steady
Qualitatively effect.When its content is higher than 12%, the decrease in transmission of the shortwave part of glass visible light region, glass coloration is bright
It is aobvious；When its content is less than 1%, it is not able to satisfy the requirement of refractive index, chemical stability also declines.Nb in the present invention5+'s
Content range is limited to 1-12%, and preferred content range is 2-10%, and further preferably range is 3-8%.
Ti in the present invention4+It can participate in glass network to be formed, and there is the work for improving glass refraction and chemical stability
With.In the present invention, Ti4+When content is 8-25%, glass has good chemical stability, and can promote refractive index.When it contains
When amount is greater than 25%, the decrease in transmission of the shortwave part of glass visible light region, glass coloration is obvious；Its content is less than 8%
When, it is not able to satisfy the requirement of refractive index, chemical stability also declines.Ti in the present invention4+Content range be limited to 8-
25%, preferred content range is 10-20%, and further preferably range is 14-20%.
The present inventor has found through numerous studies, Si4+、Zr4+Total amount and Nb5+、Ti4+Total amount there are certain proportion relationships
When, will affect glass at glass stability and devitrification resistance energy.Through further research, it has been found that as (Si4++Zr4+)/(Nb5++
Ti4+) ratio range when being limited to 0.06-2, glass can excellent, preferably (Si at glass stability and devitrification resistance4++Zr4+)/
(Nb5++Ti4+) it is 0.08-1, further preferably 0.1-0.52.
In the present invention, W6+Have the function of improving glass refraction, but when its content is greater than 10%, the chemistry of glass is steady
Qualitative, transmitance and devitrification resistance can be deteriorated.Therefore, content range is limited to 0-10%, preferably 0-5%, further
It does not contain preferably.
The present inventor has found through lot of experiments, Nb5+、Ti4+And W6+Total amount and Y3+There are when certain proportion relationship,
Glass has excellent devitrification resistance energy.As (Nb5++Ti4++W6+)/Y3+Value less than 26 when, devitrification resistance can deteriorate, when it
When value is greater than 46, chemical stability deteriorates.Therefore, ratio range is limited to 26-46, preferably 26-40, further preferably
For 28-35.
In the present invention, Li+It can increase glass melting, reduce transition temperature, when its content is more than 10%, the folding of glass
Design requirement is not achieved in the rate of penetrating, therefore its upper limit is controlled 10%.
Na in the present invention+、K+All have the function of improving the meltbility of glass.In the present invention, Na+、K+Content be greater than
When 10%, the refractive index of glass is not reached requirement, therefore Na+、K+Content be limited to 10% or less respectively.
Li in the present invention+、Na+、K+It is alkali metal ion, the optical data of adjustable glass improves the molten of glass
Melt effect, makes glass that there is lower transition temperature.As its total amount Li++Na++K+Value less than 10% when, glass has good
Chemical stability, and be able to satisfy the requirement of refractive index.When its value is greater than 10%, the devitrification resistance of glass can deteriorate.Therefore,
Li++Na++K+The range of value be limited to 0-10%, preferably 0-5%, do not contain further preferably.
In the present invention, Ba2+With glass refraction is improved, improve the effect of glass transmitance, but when its content is greater than
When 10%, the chemical stability and devitrification resistance of glass can be deteriorated.Therefore, content range is limited to 0-10%, preferably
0-5% is not contained further preferably.
In the present invention, Sr2+The refractive index and Abbe number of glass can be effectively adjusted, but its cost of material is higher, and when it contains
Amount is greater than when 10%, and the chemical stability and devitrification resistance of glass can be deteriorated.Therefore, content range is limited to 0-
10%, preferably 0-5%, do not contain further preferably.
In the present invention, Ca2+The Abbe number and specific gravity of glass can be reduced, but when its content is greater than 10%, the anti-analysis of glass
Brilliant degradation.Therefore, content range is limited to 0-10%, preferably 0-5%, does not contain further preferably.
In the present invention, Mg2+The chemical stability of glass can be promoted, but when its content is excessive, the refractive index of glass cannot
It meets the requirements, and crystallization property and chemical stability can decline.Therefore, content range is limited to 0-10%, preferably 0-
5%, it does not contain further preferably.
In the present invention, Ba2+、Sr2+、Ca2+、Mg2+It is alkaline-earth metal ions, the refractive index of glass can be adjusted, reduces glass
High temperature viscosity.Work as Ba2+、Sr2+、Ca2+、Mg2+Total amount, i.e. (Ba2++Sr2++Ca2++Mg2+) value be greater than 10% when, glass
Chemical stability and resistance crystalline substance performance be obviously deteriorated.Therefore, by (Ba2++Sr2++Ca2++Mg2+) value be limited to 0-10%, it is excellent
It is selected as 0-5%, is not contained further preferably.
Contained Main Anions are O in the present invention2-, can be in the case where not influencing the performance of optical glass of the present invention
To a certain extent containing such as F-、Cl-Deng other anion, O in optical glass of the present invention2-Content is 95% or more, preferably
98% or more, more preferably 100%.
The range of optical glass refractive index (nd) of the invention is 1.99-2.01；The Abbe number (vd) of glass of the present invention
Range is 28-31, preferred scope 28-30.
The devitrification resistance energy test method of glass in the present invention are as follows: mother glass is cut into 20 × 20 × 10mm specification,
It is put into heat preservation in the Muffle furnace that temperature is Tg+230 DEG C of temperature to preset 30 minutes, Xu Leng in heat-preservation cotton is put into after taking-up, after cooling
Observe Surface Crystallization situation.
The chemical stability of glass passes through water-fast effect stability D in the present inventionwWith acidproof effect stability DAIt indicates.This
The water-fast effect stability D of glass in inventionwMore than 2 classes, preferably 1 class；Acidproof effect stability DAMore than 2 classes, preferably
For 1 class.
Below with reference to embodiment, the invention will be further described, and mode of the invention includes but are not limited to following implementation
Example.
Embodiment 1
Present embodiments provide the preparation method of optical glass of the invention.Using carbonate, nitrate, hydroxide,
Oxide, boric acid etc. be used as raw material, raw material corresponding to optical glass element is weighed into each raw material in proportion, after being sufficiently mixed at
For Blend Stocks, which is put into platinum crucible, is heated to 1250~1450 DEG C, and clarifies stirring 3~5 hours
Become uniform melten glass afterwards, then the melten glass is poured into the mould of preheating and is kept for 2~4 hours at 600~700 DEG C
Slow cooling is carried out later, obtains each optical glass of glass No.1~33.
Embodiment 2
The performance test methods of optical glass of the invention are present embodiments provided, specifically:
Refractive index (nd) method referring to as defined in GB/T7962.1-2010 is tested；
Abbe number (vd) method referring to as defined in GB/T7962.1-2010 is tested；
The devitrification resistance energy test method of glass are as follows: mother glass is cut into 20 × 20 × 10mm specification, is put into temperature
It is 30 minutes default to be kept the temperature in the Muffle furnace of Tg+230 DEG C of temperature, it is put into Xu Leng in heat-preservation cotton after taking-up, observes surface after cooling
Crystallization situation.No obvious crystallization is denoted as " A ", has obvious crystallization to be denoted as " B ".
Water-fast effect stability DwTest method method referring to as defined in GB/T17129 tested；
Acidproof effect stability DATest method method referring to as defined in GB/T17129 tested.
Embodiment 3
The composition and performance for present embodiments providing optical glass of the invention, specifically see the table below:
Table 1
Table 2
| Component (mol%) | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 |
| Si4+ | 2.86 | 6.18 | 1.05 | 6.8 | 2.21 | 2.55 | 5.11 | 6.33 |
| B3+ | 25.42 | 30.16 | 28.64 | 28 | 32 | 26.44 | 26.22 | 28.97 |
| La3+ | 26.00 | 27.49 | 29.16 | 31.63 | 30.1 | 29.2 | 31.41 | 31.42 |
| Gd3+ | 15.00 | 3.89 | 1.37 | 9.75 | 7.0 | 3.8 | 2.14 | 2.15 |
| Y3+ | 0.64 | 0.57 | 0.71 | 0.67 | 0.95 | 0.80 | 0.85 | 0.85 |
| Zn2+ | 3.71 | 6.31 | 1.81 | 0.56 | 1.78 | 6.29 | 4.33 | 4.23 |
| Zr4+ | 4.36 | 3.93 | 1.00 | 2 | 1.01 | 9.16 | 1.98 | 2.97 |
| Nb5+ | 6.28 | 7.16 | 12.00 | 12 | 10.3 | 11.2 | 10.52 | 10.21 |
| Ti4+ | 12.49 | 9.27 | 20.00 | 8 | 14.65 | 10.56 | 17.44 | 12.87 |
| W6+ | 0.00 | 0.00 | 0.00 | 0 | 0 | 0 | 0 | 0 |
| Ba2+ | 0.00 | 1.08 | 0.00 | 0 | 0 | 0 | 0 | 0 |
| Sr2+ | 0.00 | 1.73 | 0.00 | 0.16 | 0 | 0 | 0 | 0 |
| Ca2+ | 0.00 | 1.09 | 0.49 | 0 | 0 | 0 | 0 | 0 |
| Mg2+ | 1.00 | 0.00 | 0.93 | 0 | 0 | 0 | 0 | 0 |
| Li+ | 0.00 | 1.14 | 0.00 | 0 | 0 | 0 | 0 | 0 |
| Na+ | 1.12 | 0.00 | 2.84 | 0.43 | 0 | 0 | 0 | 0 |
| K+ | 1.12 | 0.00 | 0.00 | 0 | 0 | 0 | 0 | 0 |
| It is total | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| (La3++Gd3+)/Y3+ | 64.06 | 55.05 | 43.00 | 61.76 | 39.05 | 41.25 | 39.47 | 39.49 |
| (Si4++B3+)/Y3+ | 44.19 | 63.75 | 41.82 | 51.94 | 36.01 | 36.24 | 36.86 | 41.53 |
| (Nb5++Ti4++W6+)/Y3+ | 29.33 | 28.82 | 45.07 | 29.85 | 26.26 | 27.20 | 32.89 | 27.15 |
| Si4+/(La3++Gd3++Y3+) | 0.07 | 0.19 | 0.03 | 0.16 | 0.06 | 0.08 | 0.15 | 0.18 |
| (Si4++Zr4+)/(Nb5++Ti4+) | 0.38 | 0.62 | 0.06 | 0.44 | 0.13 | 0.54 | 0.25 | 0.40 |
| La3+/(Si4++Zr4+) | 3.60 | 2.72 | 14.22 | 3.59 | 9.35 | 2.49 | 4.43 | 3.38 |
| nd | 2.0092 | 2.0013 | 2.0023 | 2.0100 | 2.0068 | 2.0023 | 2.0042 | 2.0036 |
| vd | 29.13 | 29.18 | 28.01 | 29.53 | 28.76 | 29.23 | 28.99 | 29.42 |
| Devitrification resistance energy | A | A | A | A | A | A | A | A |
| Water-resistant stability (DW) | 1 class | 1 class | 1 class | 1 class | 1 class | 1 class | 1 class | 1 class |
| Acid-resistant stability (DA) | 1 class | 1 class | 1 class | 2 classes | 2 classes | 1 class | 1 class | 1 class |
Table 3
Table 4
Embodiment 4
Present embodiments provide the method that gas preform is prepared using optical glass of the invention.By gained in table 1-4
To optical glass be cut into predefined size, then be equably coated with the release agent being made of boron nitride powder on the surface, then
It is heated, softens, be press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, biconcave lens, put down
The prefabricated component of the various lens such as convex lens, plano-concave lens, prism.
Embodiment 5
Present embodiments provide the method that optical element is prepared using gas preform of the invention.
It will anneal, be carried out while reducing the deformation of inside glass micro- by gas preform made from 4 method of embodiment
It adjusts, so that the optical characteristics such as refractive index reach desirable value.Then, each prefabricated component is ground, ground, it is saturating to make recessed falcate
The various lens, prism such as mirror, male bend moon-shaped lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.Gained optics member
Antireflection film can be also coated on the surface of part.
Embodiment 6
Optical instrument embodiment
By optical element made from above-mentioned optical element embodiment by optical design, by using one or more optics
Element forms optical component or optical module, can be used for such as imaging device, sensor, microscope, medical science, number and throws
Shadow, communication, optical communication technique/information transmission, optics/illumination in automotive field, photoetching technique, excimer laser, crystalline substance
Piece, computer chip and integrated circuit and electronic device including such circuit and chip.
Above-described embodiment is only one of the preferred embodiment of the present invention, should not be taken to limit protection model of the invention
It encloses, as long as that in body design thought of the invention and mentally makes has no the change of essential meaning or polishing, is solved
The technical issues of it is still consistent with the present invention, should all be included within protection scope of the present invention.
Claims (14)
1. optical glass, which is characterized in that it is formed is indicated by mole %, is contained: Si4+: 1-10%, B3+: 25-40%, La3+:
20-40%, Gd3+: 0-15%, Y3+: greater than 0 but be less than or equal to 10%, Zr4+: 1-10%, Nb5+: 1-12%, Ti4+: 8-25%,
Wherein (La3++Gd3+)/Y3+For 39-65.
2. optical glass according to claim 1, which is characterized in that also contain: Zn2+: 0-8%, W6+: 0-10%, R2+:
0-10%, R+: 0-10%, wherein R2+For Ba2+、Sr2+、Ca2+、Mg2+One of or a variety of, R+For Li+、Na+、K+One of
Or it is a variety of.
3. optical glass, which is characterized in that it, which is formed, is expressed as Si by a mole %4+: 1-10%, B3+: 25-40%, La3+: 20-
40%, Gd3+: 0-15%, Y3+: greater than 0 but be less than or equal to 10%, Zr4+: 1-10%, Nb5+: 1-12%, Ti4+: 8-25%, Zn2 +: 0-8%, W6+: 0-10%, R2+: 0-10%, R+: 0-10%, wherein (La3++Gd3+)/Y3+For 39-65, R2+: for Ba2+、Sr2+、
Ca2+、Mg2+One of or a variety of, R+For Li+、Na+、K+One of or it is a variety of.
4. optical glass according to claim 1 to 3, which is characterized in that each component meets following 6 kinds of situations
One of or more than one:
1)(La3++Gd3+)/Y3+For 40-60；
2)(Si4++B3+)/Y3+For 36-69；
3)(Nb5++Ti4++W6+)/Y3+For 26-46；
4)Si4+/(La3++Gd3++Y3+) it is 0.02-0.4；
5)(Si4++Zr4+)/(Nb5++Ti4+) it is 0.06-2；
6)La3+/(Si4++Zr4+) it is 1.5-15.
5. optical glass according to claim 1 to 3, which is characterized in that wherein Si4+: 3-9%, and/or B3+:
26-35%, and/or La3+: 25-35%, and/or Gd3+: 0-10%, and/or Y3+: 0.1-5%, and/or Zr4+: 1-8% and/
Or Nb5+: 2-10%, and/or Ti4+: 10-20%, and/or Zn2+: 0.1-5%, and/or W6+: 0-5%, and/or R2+: 0-5%,
And/or R+: 0-5%, wherein R2+: for Ba2+、Sr2+、Ca2+、Mg2+One of or a variety of, R+For Li+、Na+、K+One of or
It is a variety of.
6. optical glass according to claim 1 to 3, which is characterized in that each component meets in following 6 kinds of situations
It is one or more kinds of:
1)(La3++Gd3+)/Y3+For 42-55；
2)(Si4++B3+)/Y3+For 40-65；
3)(Nb5++Ti4++W6+)/Y3+For 26-40；
4)Si4+/(La3++Gd3++Y3+) it is 0.05-0.3；
5)(Si4++Zr4+)/(Nb5++Ti4+) it is 0.08-1；
6)La3+/(Si4++Zr4+) it is 2-10.
7. optical glass according to claim 1 to 3, which is characterized in that wherein Si4+: 4-8%, and/or B3+: 27-
32%, and/or La3+: 26-33%, and/or Gd3+: 1-8%, and/or Y3+: 0.3-3%, and/or Zr4+: 2-6%, and/or Nb5 +: 3-8%, and/or Ti4+: 14-20%, and/or Zn2+: 1-4%.
8. optical glass according to claim 1 to 3, which is characterized in that each component meets in following 5 kinds of situations
It is one or more kinds of:
1)(Si4++B3+)/Y3+For 45-58；
2)(Nb5++Ti4++W6+)/Y3+For 28-35；
3)Si4+/(La3++Gd3++Y3+) it is 0.08-0.21；
4)(Si4++Zr4+)/(Nb5++Ti4+) it is 0.1-0.52；
5)La3+/(Si4++Zr4+) it is 2.42-8.
9. optical glass according to claim 1 to 3, which is characterized in that do not contain W6+And/or R2+And/or R+。
10. optical glass according to claim 1 to 3, which is characterized in that the refractive index (nd) of the glass is
1.99-2.01 Abbe number (vd) is 28-31.
11. optical glass according to claim 1 to 3, which is characterized in that the acidproof effect stability of the glass
(DA) it is 2 classes or more, preferably 1 class；The water-fast effect stability (D of the glassW) it is 2 classes or more, preferably 1 class.
12. gas preform, which is characterized in that the optical glass described in claim 1-11 any one is made.
13. optical element, which is characterized in that the optical glass described in claim 1-11 any one is made or right is wanted
Gas preform described in asking 12 is made.
14. optical instrument, which is characterized in that include the optical element described in claim 13.
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| CN101613184A (en) * | 2008-06-27 | 2009-12-30 | Hoya株式会社 | Opticglass |
| CN102030473A (en) * | 2009-09-30 | 2011-04-27 | Hoya株式会社 | Optical glass, preform for precision press molding, optical element and manufacturing process thereof |
| CN102219374A (en) * | 2010-04-15 | 2011-10-19 | Hoya株式会社 | Optical glass, preform for precision press molding, optical element, method for manufacturing optical element |
| CN104136388A (en) * | 2012-02-28 | 2014-11-05 | Hoya株式会社 | Optical glass and use thereof |
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| TWI649292B (en) * | 2012-06-29 | 2019-02-01 | 日商小原股份有限公司 | Optical glass, optical element and preform |
| CN105837028B (en) * | 2015-04-10 | 2019-03-12 | 成都光明光电股份有限公司 | Optical glass |
| CN106698926A (en) * | 2016-09-30 | 2017-05-24 | 成都光明光电股份有限公司 | Optical glass, glass prefabricated part, optical element and optical instrument |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101613184A (en) * | 2008-06-27 | 2009-12-30 | Hoya株式会社 | Opticglass |
| CN102030473A (en) * | 2009-09-30 | 2011-04-27 | Hoya株式会社 | Optical glass, preform for precision press molding, optical element and manufacturing process thereof |
| CN102219374A (en) * | 2010-04-15 | 2011-10-19 | Hoya株式会社 | Optical glass, preform for precision press molding, optical element, method for manufacturing optical element |
| CN104136388A (en) * | 2012-02-28 | 2014-11-05 | Hoya株式会社 | Optical glass and use thereof |
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| CN109665714A (en) * | 2019-02-28 | 2019-04-23 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
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