CN110156323A - Fluorphosphate glass, gas preform, optical element and the optical instrument with it - Google Patents
Fluorphosphate glass, gas preform, optical element and the optical instrument with it Download PDFInfo
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- CN110156323A CN110156323A CN201910473376.7A CN201910473376A CN110156323A CN 110156323 A CN110156323 A CN 110156323A CN 201910473376 A CN201910473376 A CN 201910473376A CN 110156323 A CN110156323 A CN 110156323A
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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
- C03C3/12—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
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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
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Abstract
The invention discloses a kind of fluorphosphate glass, gas preform, optical elements and with its optical instrument, and the fluorphosphate glass includes: cation and anion, the cation include: the P that the cation includes: 25~40 moles of %5+；The Al of 8~22 moles of %3+；The La of 0~8 mole of %3+；The Y of 1~10 mole of %3+；The Sr of 3~15 moles of %2+；The Ba of 25~40 moles of %2+；The Gd of 1~10 mole of %3+；The anion includes: the F of 38~50 moles of %‑；The O of 50~62 moles of %2‑, wherein
Description
Technical field
The invention belongs to fluorphosphate glass technical fields, specifically, the present invention relates to fluorphosphate glass, glass are pre-
Product, optical element and the optical instrument with it.
Background technique
Fluorophosphate optical glass is a kind of special optical glass of low dispersion, can eliminate second order spectrum color difference, improve
The image quality of optical lens, while there is lower softening point, non-spherical lens can be made by primary or secondary press,
It is the better optical material for producing advanced digital product.
Current most of fluorphosphate glass stress optical coefficients are big, and glass thermal stability under strong light is bad, in temperature
Rise very fast, inside glass is easy to produce stress, to reduce imaging image quality, or even be not imaged, thus refractive index nd 1.52~
1.60, the colourless fluorphosphate glass of the low dispersion of higher refractive that Abbe number vd is not less than 68 and stress optical coefficient is small, market need
Ask urgent.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of fluorphosphate glass, gas preform, optical element and the optical instrument with it, the fluorine phosphorus
For the refractive index of silicate glass 1.52~1.60, Abbe number is not less than 68, and has excellent optical property etc., has simultaneously
Lower thermal refractive index coefficient, thus the excellent heat stability under strong light, inside glass is not likely to produce stress, and then improves it
Image quality is imaged, meets market needs.
In one aspect of the invention, the invention proposes a kind of fluorphosphate glasses.According to an embodiment of the invention, institute
Stating fluorphosphate glass includes: cation and anion, wherein the cation includes: the P of 25~40 moles of %5+；8~22
The Al of mole %3+；The La of 0~8 mole of %3+；The Y of 1~10 mole of %3+；The Sr of 3~15 moles of %2+；25~40 moles of %'s
Ba2+；The Gd of 1~10 mole of %3+；The anion includes: the F of 38~50 moles of %-；The O of 50~62 moles of %2-, wherein
n(Y 3++La 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )Greater than 0.07.
Inventors have found that by controlling the usage ratio between its component, content and specific components, so that fluorine of the invention
For the refractive index of phosphate glass 1.52~1.60, Abbe number is not less than 68, and has excellent optical property etc., has simultaneously
There is lower refractive index high temperature coefficient, thus the excellent heat stability under strong light, inside glass is not likely to produce stress, and then improves
Image quality is imaged in it, meets market needs.
In addition, fluorphosphate glass according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, cation described in above-mentioned fluorphosphate glass composition includes: 30~37 to rub
The P of your %5+, the P of preferably 31~36 moles %5+；And/or the Al of 10~20 moles of %3+, the Al of preferably 12~17 moles %3+；
And/or the La of 0~5 mole of %3+, be free of endpoint 0, the La of preferably 0.5~4 mole %3+；And/or the Gd of 1~6 mole of %3+, excellent
Select the Gd of 1~5 mole of %3+；And/or the Y of 1~8 mole of %3+, the Y of preferably 2~6 moles %3+；And/or 28~38 moles of %
Ba2+, the Ba of preferably 30~35 moles %2+；And/or the Sr of 5~12 moles of %2+, the Sr of preferably 5~10 moles %2+.As a result, may be used
To guarantee that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, anion described in above-mentioned fluorphosphate glass composition includes: 41~48 to rub
The F of your %-, the F of preferably 42~46 moles %-；And/or the O of 52~59 moles of %2-, the O of preferably 54~58 moles %2-.By
This, it is ensured that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, in above-mentioned fluorphosphate glass composition, n(Y 3++La 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )
=0.075~0.5.Thus, it is possible to guarantee that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, cation described in above-mentioned fluorphosphate glass composition further comprises: 0~
The Yb of 10 moles of %3+, the Yb of preferably 0~5 mole %3+；And/or the Ca of 0~10 mole of %2+, the Ca of preferably 0~5 mole %2+；
And/or the Mg of 0~10 mole of %2+, the Mg of preferably 0~5 mole %2+.Thus, it is possible to which it is excellent to guarantee that the fluorphosphate glass has
Different performance.
In some embodiments of the invention, in above-mentioned fluorphosphate glass composition, n(Y 3+ +La 3+ )/n(Sr 2+ +Ba 2+ )It is greater than
0.11, preferably greater than 0.135, more preferable 0.14~0.65, n(Sr 2++Y 3+ )/n(Al 3+ +Ba 2+ )=0.25~0.43, be free of endpoint
0.25, preferably 0.265~0.375, be free of endpoint 0.265.Thus, it is possible to guarantee that the fluorphosphate glass has excellent property
Energy.
In some embodiments of the invention, in above-mentioned fluorphosphate glass composition, n(Y 3++Gd 3++Ba 2+ )/n(P 5+ +Al 3+ +Sr 2+
+Ba 2+ )=0.435~0.505, preferably 0.44~0.5.Thus, it is possible to guarantee that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, in above-mentioned fluorphosphate glass composition, n(sr 2++Ba 2+ )/n(Y 3+ +Gd 3+ +La 3+ )=
3.45~9, preferably 3.45~7.6, more preferable 3.55~5.55.Thus, it is possible to which it is excellent to guarantee that the fluorphosphate glass has
Performance.
In some embodiments of the invention, cation described in above-mentioned fluorphosphate glass composition further comprises: 0~
The Li of 15 moles of %+, the Li of preferably 0~10 mole %+；And/or the Na of 0~15 mole of %+, the Na of preferably 0~10 mole %+；
And/or the K of 0~10 mole of %+, the K of preferably 0~5 mole %+；And/or the B of 0~8 mole of %3+, the B of preferably 0~5 mole %3 +；And/or the Zn of 0~10 mole of %2+, the Zn of preferably 0~5 mole %2+；And/or the In of 0~8 mole of %3+, preferably 0~5 rubs
The In of your %3+；And/or the Nb of 0~5 mole of %5+, the Nb of preferably 0~3 mole %5+；And/or the Ti of 0~5 mole of %4+, preferably
The Ti of 0~3 mole of %4+；And/or the Zr of 0~5 mole of %4+, the Zr of preferably 0~3 mole %4+；And/or 0~5 mole of %
Ta5+, the Ta of preferably 0~3 mole %5+；And/or the Ge of 0~5 mole of %4+, the Ge of preferably 0~3 mole %4+.Thus, it is possible to protect
The fluorphosphate glass is demonstrate,proved with excellent performance.
In some embodiments of the invention, above-mentioned fluorphosphate glass refractive index be 1.52~1.60, preferably 1.53~
1.58, more preferable 1.55~1.58, Abbe number is 68~75, preferably 69~74, more preferable 70~73.
In some embodiments of the invention, the refractive index temperature of the fluorphosphate glass of above-mentioned fluorphosphate glass
Coefficient is -4.0 × 10-6/ degree Celsius hereinafter, it is preferred that -5.0 × 10-6/ degree Celsius hereinafter, more preferably -7.5 × 10-6/ degree Celsius with
Under, λ80No more than 370nm, preferably no greater than 360nm, more preferably no more than 350nm, λ5No more than 310nm, preferably no greater than
300nm, more preferably no more than 295nm.
In some embodiments of the invention, the density of above-mentioned fluorphosphate glass is not higher than 4.7g/cm3, preferably not high
In 4.6g/cm3, more preferably no higher than 4.5g/cm3, stress optical coefficient is not higher than 0.6 × 10-12/ Pa, preferably no greater than 0.5 ×
10-12/ Pa, more preferably no higher than 0.4 × 10-12/ Pa, abrasion degree are not higher than 500, preferably no greater than 450, acidproof effect stability
Not less than 2 grades, preferably not less than 1 grade, water-fast effect stability is not less than 2 grades, preferably not less than 1 grade.
In another aspect of the invention, the invention proposes a kind of gas preforms.According to an embodiment of the invention, institute
Gas preform is stated to be made of above-mentioned fluorphosphate glass.
In the third aspect of the invention, the invention proposes a kind of optical elements.According to an embodiment of the invention, described
Optical element is made of above-mentioned fluorphosphate glass or above-mentioned gas preform.
In the fourth aspect of the invention, the invention proposes a kind of optical instruments.According to an embodiment of the invention, described
Optical instrument has above-mentioned optical element.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail, the embodiments described below is exemplary, it is intended to for explaining this
Invention, and be not considered as limiting the invention.
Unless in particular situations it is further noted that numberical range listed herein includes upper limit value and lower limit value, " with
On " and " following " include endpoint value, all integers and score in the range, and be not limited to tool listed when limited range
Body value.Herein referred "and/or" is inclusive, such as " A and/or B ", refers to only A, perhaps only B or has A simultaneously
And B.
It should be noted that the ioni valence of each ingredient described below be for convenience and the typical value that uses, with other
Ioni valence be not different.A possibility that ioni valence of each component is there are other than typical value in optical glass.For example, P usually with
Ioni valence is present in glass for the state of+5 valences, therefore in the present invention with " P5+" it is used as typical value, but exist with other
Ioni valence state there are a possibility that, this is also within protection scope of the present invention.
In one aspect of the invention, the invention proposes a kind of fluorphosphate glasses.According to an embodiment of the invention, institute
State fluorphosphate glass include: cation and anion, the cation include: the P of 25~40 moles of %5+；8~22 moles of %
Al3+；The La of 0~8 mole of %3+；The Y of 1~10 mole of %3+；The Sr of 3~15 moles of %2+；The Ba of 25~40 moles of %2+；1
The Gd of~10 moles of %3+；The anion includes: the F of 38~50 moles of %-；The O of 50~62 moles of %2-, wherein n(Y 3+
+La 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )Greater than 0.07.It should be noted that component molar % is the cation and all sun in cation
The ratio of ion total mole number, similarly in anion component molar % be the anion and all anion total mole numbers ratio
Value.
Glass ingredient:
P5+It is the important component in fluophosphate glass for reducing dispersion, and is that the imaging of influence glass and outdoor high temperature are resistance to
Main component.When its introduction volume is lower than 25 moles of %, stability, glass is reduced, and tendency towards devitrification increases, and it is reflected
Rate temperature coefficient is lower, but when its introduction volume is higher than 40 moles of %, is unable to satisfy scheduled optical property.Therefore, of the invention
P5+Content be 25~40 moles of %, preferably P5+Content be 30~37 moles of %, more preferable 31~36 moles of %.
Al3+It is the constituent in fluophosphate glass as network skeleton, and for improving into the important of glass stability
Ingredient.When its introduction volume is lower than 8 moles of %, stability, glass is lower, but when its introduction volume is higher than 22 moles of %, glass turns
Temperature and crystallization ceiling temperature increase significantly, and forming temperature is caused to increase.Therefore, Al of the invention3+Content be 8~22 to rub
You are %, preferably Al3+Content be 10~20 moles of %, more preferable 12~17 moles of %.
La3+、Gd3+、Y3+And Yb3+It can be improved the refractive index of glass, but Ln3+(it is selected from La3+、Gd3+、Y3+And Yb3+In
At least one of) when being lower than 1 mole of %, smaller, but Ln is influenced on the refractive index of glass3+When higher than 30 moles of %, glass will lead to
The stability of glass deteriorates, while glass transformation temperature is increased, and the stability of glass is caused to reduce.Therefore, Ln of the invention3+
For 1~30 mole of %, preferably 2~20 moles of %, more preferable 3~15 moles of %, wherein the La including 0~8 mole of %3+, preferably
The La of 0~5 mole of %3+, be free of endpoint 0, the La of more preferable 0.5~4 mole of %3+；And/or the Gd of 1~10 mole of %3+, preferably
The Gd of 1~6 mole of %3+, the Gd of more preferable 1~5 mole of %3+；And/or the Y of 1~10 mole of %3+, preferably 1~8 mole of %'s
Y3+, the Y of more preferable 2~6 moles of %3+；And/or the Yb of 0~10 mole of %3+, the Yb of preferably 0~5 mole %3+, do not draw more preferably
Enter.
Ba2+、Ca2+、Sr2+And Mg2+The stability and refractive index of glass, but R can be improved2+(it is selected from Ba2+、Ca2+、Sr2+
And Mg2+At least one of) when being lower than 25 moles of %, the stability of the stability of glass and glass is improved influence it is unobvious,
But R2+When higher than 55 moles of %, the stability of glass is caused sharply to decline, and can also significantly reduce glass dispersion.As a result, originally
The R of invention2+For 25~55 moles of %, preferably 30~50 moles of %, more preferable 35~45 moles of % can improve refractive index
Meanwhile will not be excessive reduction glass dispersion, wherein the Ba including 25~40 moles of %2+, preferably 28~38 moles of %'s
Ba2+, the Ba of more preferable 30~35 moles of %2+；And/or the Ca of 0~10 mole of %2+, the Ca of preferably 0~5 mole %2+, more preferably
It does not introduce；And/or the Sr of 3~15 moles of %2+, the Sr of preferably 5~12 moles %2+, the Sr of more preferable 5~10 moles of %2+；With/
Or the Mg of 0~10 mole of %2+, the Mg of preferably 0~5 mole %2+, do not introduce more preferably.
F-Fusing point and the dispersion of glass can be reduced, and the thermal refractive index coefficient of glass can also be reduced.When its introducing
When amount is lower than 38 moles of %, the fusing point of glass is higher, leads to its poor processability, while the high temperature resistance of glass is poor,
But when its introduction volume is higher than 50 moles of %, glass volatility in fusion process is increased, and glass loss increases, and reflects forthright
It can also be deteriorated.Therefore, F of the invention-Content be 38~50 moles of %, preferably F-Content be 41~48 moles of %, more preferably
42~46 moles of %.
O2-It is the necessary component of glass network structure, stability, glass can be improved, inhibit the devitrification of glass, reduces abrasion
Degree.When its introduction volume is lower than 50 moles of %, inhibit the devitrification of glass and wear intensity effect unobvious, but when its introduction volume is high
When 62 moles of %, so that the viscosity of glass rises and melting temperature increases, transmitance is caused to deteriorate.Therefore, O of the invention2-
Content be 50~62 moles of %, preferably O2-Content be 52~59 moles of %, more preferable 54~58 moles of %.
Inventors have found that the fluorphosphate glass of the application requires higher refractive index and optical characteristics and lower
Dispersion, while there is lower stress optical coefficient and thermal refractive index coefficient etc., and the inventors of the present application found that passing through
Control Y in glass ingredient3+And La3+Total molal quantity and P5+And Al3+、Sr2+、Y3+The ratio between total molal quantity (n(Y 3++La 3+ )/
n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )) it is greater than 0.07, it acts synergistically between each component, the refractive index and optical property of glass can be improved, and
And dispersion and stress optical coefficient are reduced, and glass temporary stress is easy to eliminate, and imaging is more stable, and thermal refractive index coefficient is small, folding
It is high to penetrate rate stability, is more suitable for the use of outdoor high temperature environment, specifically, the refractive index of gained fluorphosphate glass be 1.52~
1.60, Abbe number is 68~75, and thermal refractive index coefficient is -4.0 × 10-6/ degree Celsius hereinafter, stress optical coefficient is not higher than
0.6×10-12/ Pa, λ80No more than 370nm, λ5Y in glass ingredient is further preferably controlled no more than 310nm3+And La3+Conjunction
Count molal quantity and P5+And Al3+、Sr2+、Y3+The ratio between total molal quantity (n(Y 3++La 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )) it is 0.075~0.5,
Obtain fluorphosphate glass refractive index be 1.53~1.58, preferably 1.55~1.58, Abbe number be 69~74, preferably 70~
73, thermal refractive index coefficient is -5.0 × 10-6/ degree Celsius hereinafter, preferably -7.5 × 10-6/ degree Celsius hereinafter, stress optics
Coefficient is not higher than 0.5 × 10-12/ Pa, preferably no greater than 0.4 × 10-12/ Pa, λ80No more than 360nm, preferably no greater than 350nm,
λ5No more than 300nm, preferably no greater than 295nm.
Meanwhile the fluorphosphate glass of the application require it is excellent at glass stability and water-fast acidproof effect is stablized
Performance, lower wear intensity etc., and present inventor is had found by numerous studies, by controlling La in glass ingredient simultaneously3+
And Y3+Total molal quantity and Ba2+And Sr2+The ratio between total molal quantity n(Y 3+ +La 3+ )/n(Sr 2+ +Ba 2+ )Greater than 0.11, Sr2+And Y3+'s
Total molal quantity and Al3+And Ba2+The ratio between total molal quantity (n(Sr 2++Y 3+ )/n(Al 3+ +Ba 2+ )) it is 0.25~0.43, be free of endpoint
0.25, synergistic effect is played between each component, can be further improved the refractive index of glass, at glass stability and optical characteristics,
And dispersion, thermal refractive index coefficient are further decreased, while improving acidproof water-fast effect stability and wear-resisting property, it obtains
The acidproof effect stability of fluorophosphate is not less than 2 grades, and water-fast effect stability is not less than 2 grades, and abrasion degree is not higher than 500, into one
N in the preferred control glass ingredient of step(Y 3+ +La 3+ )/n(Sr 2+ +Ba 2+ )Greater than 0.135, preferably 0.14~0.65；n(Sr 2++Y 3+ )/
n(Al 3+ +Ba 2+ )=0.265~0.375, endpoint 0.265 is free of, the acidproof effect stability of gained fluorphosphate glass is not less than 1 grade,
Water-fast effect stability is not less than 1 grade, and abrasion degree is not higher than 450.
Further, the fluorphosphate glass of the application it is also desirable to have lower specific gravity, inventors have found that passing through control
Y in glass ingredient3+And Gd3+、Ba2+Total molal quantity and P5+And Al3+、Sr2+、Ba2+The ratio between total molal quantity (n(Y 3++Gd 3+
+Ba 2+ )/n(P 5+ +Al 3+ +Sr 2++Ba 2+ )) it is 0.435~0.505, being more advantageous to reduces F volatilization, and the optics for further increasing glass is special
Property and stable refractive index, and reduce specific gravity of glass, the density of obtained fluorphosphate glass is not higher than 4.7g/cm3, preferably
Control Y in glass ingredient3+And Gd3+、Ba2+Total molal quantity and P5+And Al3+、Sr2+、Ba2+The ratio between total molal quantity (n(Y 3+
+Gd 3++Ba 2+ )/n(P 5+ +Al 3+ +Sr 2++Ba 2+ )) it is 0.44~0.5, the density of obtained fluorphosphate glass is not higher than 4.6g/cm3, excellent
Choosing is not higher than 4.5g/cm3。
Further, inventor also found, pass through Sr in control glass ingredient2+And Ba2+Total molal quantity and Y3+、Gd3+
And La3+The ratio between total molal quantity (n(sr 2++Ba 2+ )/n(Y 3+ +Gd 3+ +La 3+ )) be 3.45~9, can be further improved glass at glass
Stability, and dispersion will not be excessively reduced while improving glass refraction, preferably Sr in control glass ingredient2+And Ba2+
Total molal quantity and Y3+、Gd3+And La3+The ratio between total molal quantity (n(sr 2++Ba 2+ )/n(Y 3+ +Gd 3+ +La 3+ )) it is 3.45~7.6, more
It is preferred that 3.55~5.55.
According to still another embodiment of the invention, cation further comprises in above-mentioned fluorphosphate glass composition: 0~15
The Li of mole %+, the Li of preferably 0~10 mole %+；And/or the Na of 0~15 mole of %+, the Na of preferably 0~10 mole %+；
And/or the K of 0~10 mole of %+, the K of preferably 0~5 mole %+；And/or the B of 0~8 mole of %3+, the B of preferably 0~5 mole %3 +；And/or the Zn of 0~10 mole of %2+, the Zn of preferably 0~5 mole %2+；And/or the In of 0~8 mole of %3+, preferably 0~5 rubs
The In of your %3+；And/or the Nb of 0~5 mole of %5+, the Nb of preferably 0~3 mole %5+；And/or the Ti of 0~5 mole of %4+, preferably
The Ti of 0~3 mole of %4+；And/or the Zr of 0~5 mole of %4+, the Zr of preferably 0~3 mole %4+；And/or 0~5 mole of %
Ta5+, the Ta of preferably 0~3 mole %5+；And/or the Ge of 0~5 mole of %4+, the Ge of preferably 0~3 mole %4+.Inventors have found that
Li+Glass transformation temperature can be reduced without damage stability, glass, when its introduction volume is higher than 35 moles of %, the stability of glass
It reduces, and the poor processability of glass.Therefore, Li of the invention+Content be 0~15 mole of %, preferably Li+Content
For 0~10 mole of %, do not introduce more preferably.Na+The meltbility of glass, devitrification resistance can be improved and improve the saturating of visible light region
Rate is crossed, but when its introduction volume is higher than 15 moles of %, the stability of glass is reduced.Therefore, Na of the invention+Content be 0~
15 moles of %, preferably 0~10 mole of %, do not introduce more preferably.K+The viscosity and transition temperature of glass can be reduced, but it is introduced
When amount is higher than 10 moles of %, the stability that will lead to glass is reduced.Therefore, K of the invention+Content be 0~10 mole of %, it is excellent
0~5 mole of % is selected, is not introduced more preferably.B3+It can be improved the stability of glass, but when its introduction volume is higher than 8 moles of %, by
It is easy in melting process with BF in it3Form volatilization, and therefore cause striped.Therefore, B of the invention3+Content be 0~8
Mole %, preferably 0~5 mole of %, do not introduce more preferably.Zn2+The devitrification resistance, stability and processability that glass can be improved, when
Its introduction volume is higher than 10 moles of %, so that the devitrification resistance of glass is remarkably decreased instead.Therefore, Zn of the invention2+Content be 0
~10 moles of %, preferably Zn2+Content be 0~5 mole of %, do not introduce more preferably.In3+Stability, glass can be improved, but work as it
When introduction volume is higher than 8 moles of %, the stability of glass is caused sharply to decline.Therefore, In of the invention3+Content be 0~8 to rub
You are %, preferably In3+Content be 0~5 mole of %, do not introduce more preferably.Nb5+And Ti4+The refractive index of glass can be improved, but
It is Nb5+And Ti4+Introduction volume respectively more than 5 moles of % when, can reduce the stability of glass, therefore, Nb of the invention5+'s
Content is 0~5 mole of %, and preferably 0~3 mole of % is not introduced more preferably, Ti4+Content be 0~5 mole of %, preferably 0~3 rubs
You are %, does not introduce more preferably.Zr4+The refractive index of glass can be improved, and be able to suppress due in glass ingredient volatilization and
Caused glass vein, but its introduction volume be higher than 5 moles of % when, the stability of glass, therefore Zr of the invention can be reduced4+'s
Content is 0~5 mole of %, and preferably 0~3 mole of % is not introduced more preferably.Ta5+The refractive index of glass can be improved and reduce glass
The increased devitrification resistance of glass, but its introduction volume be higher than 5 moles of % when, the stability of glass can be reduced, therefore, Ta of the invention5+Content
For 0~5 mole of %, preferably 0~3 mole of %, do not introduce more preferably.Ge4+The refractive index and devitrification resistance of glass can be improved, but
When being that its introduction volume is higher than 5 moles of %, the raising of glass cost, therefore, Ge of the invention will lead to4+Content is 0~5 mole of %,
0~3 mole is introduced, is not introduced more preferably.
Refer to it should be noted that " not including " " not containing " " not introducing " " 0% " documented by the present invention without intentional
The compound, molecule or element etc. are added in glass of the invention as raw material；But as production glass raw material and/
Or equipment, can exist certain is not the impurity deliberately added or component, a small amount of or trace can be contained in final glass, such
Situation is also in the scope of protection of the patent of the present invention.
In the following, the performance and test method to fluorphosphate glass of the invention are illustrated.
1, degree of staining (λ80/λ5)
The shortwave transmitted spectrum characteristic degree of staining (λ of glass of the present invention80/λ5) indicate.λ80Refer to that glass transmittance reaches
Corresponding wavelength, λ when 80%5Refer to that glass transmittance reaches corresponding wavelength when 5%, wherein λ80Measurement be using having
The glass with a thickness of 10 ± 0.1mm of two parallel to each other and optical polish opposite planes, measures from 280nm to 700nm
Spectral transmission in wavelength domain and the wavelength for showing transmissivity 80%.So-called spectral transmission or transmissivity are to glass
Above-mentioned surface vertically incident intensity IinLight, project intensity I through glass and from planeoutLight in the case where lead to
Cross Iout/IinThe amount of expression, and also contain the transmissivity of the surface reflection loss on the above-mentioned surface of glass.The folding of glass
It is higher to penetrate rate, surface reflection loss is bigger.Therefore, in optical glass of the invention, λ80The small glass itself of meaning of value
Coloring is few.Optical glass transmittance of the invention reaches corresponding wavelength (λ when 80%80) it is not more than 370nm, preferably no greater than
360nm, more preferably no more than 350nm, glass transmittance reach corresponding wavelength (λ when 5%5) it is not more than 310nm, preferably not
Greater than 300nm, more preferably no more than 295nm.
Use the glass sample with a thickness of 10 ± 0.1mm with two optical polish planes relative to each other, measurement point
Light transmission is calculated according to its result.
2, density
The density of fluorphosphate glass be temperature be 20 DEG C when unit volume weight, unit is with g/cm3It indicates, the present invention
Fluorphosphate glass density be not higher than 4.7g/cm3, preferably no greater than 4.6g/cm3, more preferably no higher than 4.5g/cm3。
It is measured by method as defined in GB/T7962.20-2010.
3, refractive index and Abbe number
The refractive index nd of fluorphosphate glass of the present invention is 1.52~1.60, preferably 1.53~1.58, more preferable 1.55
~1.58, Abbe number vd are 68~75, preferably 69~74, more preferably 70~73.
Refractive index and Abbe number are tested according to method as defined in GB/T7962.1-2010.
4, thermal refractive index coefficient
The thermal refractive index coefficient of glass of the present invention is -4.0 × 10-6/ degree Celsius hereinafter, it is preferred that -5.0 × 10-6/ Celsius
Degree is hereinafter, more preferably -7.5 × 10-6/ degree Celsius or less.
Thermal refractive index coefficient is tested according to GB/T 7962.4-2010 prescriptive procedure, the refractive index of -40~80 DEG C of measurement
Temperature coefficient.
5, chemical stability (water-fast effect stability DW, acidproof effect stability DA)
For optical glass device during manufacture and use, polished surface resists the various etching medium effects such as water, acid
Ability be known as the chemical stability of optical glass, depend primarily on the chemical constituent of glass, optical glass of the invention
Water-fast effect stability Dw (powder method) is not less than 2 grades, preferably not less than 1 grade；Acidproof effect stability DA (powder method) is not low
In 2 grades, preferably not less than 1 grade.
Water-fast effect stability Dw and acidproof effect stability DA is tested by the test method of GB/T 17129.
6, stress optical coefficient
The stress optical coefficient of glass of the present invention is lower than 0.6 × 10-12/ Pa, preferably shorter than 0.5 × 10-12/ Pa, more preferably
Lower than 0.4 × 10-12/Pa。
Stress optical coefficient is tested according to following progress:
Sample requirement
Sample is processed into cylindric, both ends light pass surface polishing, and cylindrical side fine grinding, can also having a size of Φ 20mm × 15mm
Other specifications, the two light pass surface depth of parallelism≤1/100, circularity≤5/100, side taper≤1/ are processed into according to testing equipment situation
100。
Test method
The test of stress optical coefficient uses disk diametral compression sample, by cylindrical sample with nose circle face vertical optical path
Mode is put into stress birfringence optical system for testing, opposite on two endpoints that cylindrical side corresponds to a diameter D in nose circle face
Apply active force P simultaneously, keeps sample position constant, while testing the stress birefringence optical path difference δ at center location.By formulaPhotoelastic coefficient is calculated, wherein D is cylindrical samples light pass surface diameter, is measured using micrometer；P is to be applied to
Load on cylindrical samples side can be obtained by pressure gauge；δ be optical path perpendicular through sample light pass surface when birefringent light
Path difference can be measured with stress gauge.In order to improve precision, reduction error is generally corresponding two-fold using it is tested under different load
The multiple measurement method of optical path difference is penetrated, δ-P curve is drawn, then carries out linear regression processing, obtain the straight slope, Jin Erji
Calculate stress optical coefficient B.
In the second aspect of the invention, the invention proposes a kind of gas preforms.According to an embodiment of the invention, institute
Gas preform is stated to be made of above-mentioned fluorphosphate glass.Optical precast product of the invention has the spies such as low dispersion as a result,
Property, while there is lower refractive index high temperature coefficient, thus the excellent heat stability under strong light, inside glass, which is not likely to produce, is answered
Power, and then improve it and image quality is imaged, it is useful on various optical elements and optical design.It is particularly preferred to by the present invention
Fluorphosphate glass set out, the optical elements such as camera lens, prism, reflecting mirror are made using means such as precision press moldings.It needs
It is noted that above-mentioned be equally applicable to the gas preform for feature and advantage described in fluorphosphate glass, herein
It repeats no more.
In the third aspect of the invention, the invention proposes a kind of optical elements.According to an embodiment of the invention, described
Optical element is made of above-mentioned fluorphosphate glass or above-mentioned gas preform.Optical element of the invention has as a result,
Low dispersion characteristics, while there is lower refractive index high temperature coefficient, so that the excellent heat stability under strong light, inside glass are not easy
Stress is generated, and then improves it and image quality is imaged, is capable of providing the optical elements such as various lens, the prism haveing excellent performance.For example, this
The optical element of invention can be the various lens such as spherical lens, non-spherical lens, lenticule, diffraction grating, band diffraction grating
Lens, lens array, prism etc..In addition, antireflection film, total reflection film, part can be arranged on the optical element when necessary
The optical thin films such as reflectance coating, film with dichroism.It should be noted that above-mentioned be directed to fluorphosphate glass and prefabricated glass
Feature and advantage described in part are equally applicable to the optical element, and details are not described herein again.
In the fourth aspect of the invention, the invention proposes a kind of optical instruments.According to an embodiment of the invention, described
Optical instrument has above-mentioned optical element.As a result, by using the above-mentioned optics with excellent properties on the optical instrument
Element can be adapted for outdoor hot environment.Specifically, optical instrument of the invention can be in camera, projector etc.
Make the optical instrument of visible light-transmissive.It should be noted that above-mentioned equally suitable for feature and advantage described in optical element
For the optical instrument, details are not described herein again.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Glass in order to obtain with composition shown in 1~table of table 5 prepares melting and the molding side of optical glass of the present invention
Method can be using well known to a person skilled in the art technologies.Such as: by glass raw material (fluoride, carbonate, nitrate, inclined phosphorus
Hydrochlorate, oxide etc.) it weighs according to the proportion of glass ion with merging after mixing, put into (such as platinum earthenware in smelting apparatus
Crucible), then taken at 800~1250 DEG C it is appropriate stirring, clarification, homogenizing after, be cooled to 900 DEG C hereinafter, casting or leakage note exist
In molding die, the post-processings such as last annealed, processing, or formed by precise compression molding technology direct pressing.In addition, logical
Cross it is above-mentioned shown in method measure the characteristic of each glass, and measurement result is indicated in 1~table of table 5.
Table 1
Table 2
Table 3
Table 4
Table 5
Note: total amount 100% is the number deducted after measurement error, equipment precision and inevitable impurity in above table
According to.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (15)
1. a kind of fluorphosphate glass characterized by comprising cation and anion,
The cation includes:
The P of 25~40 moles of %5+；
The Al of 8~22 moles of %3+；
The La of 0~8 mole of %3+；
The Y of 1~10 mole of %3+；
The Sr of 3~15 moles of %2+；
The Ba of 25~40 moles of %2+；The Gd of 1~10 mole of %3+；
The anion includes:
The F of 38~50 moles of %-；
The O of 50~62 moles of %2-,
Wherein, n(Y 3++La 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )Greater than 0.07.
2. fluorphosphate glass according to claim 1, which is characterized in that the cation includes:
The P of 30~37 moles of %5+, the P of preferably 31~36 moles %5+；And/or
The Al of 10~20 moles of %3+, the Al of preferably 12~17 moles %3+；And/or
The La of 0~5 mole of %3+, be free of endpoint 0, the La of preferably 0.5~4 mole %3+；And/or
The Gd of 1~6 mole of %3+, the Gd of preferably 1~5 mole %3+；And/or
The Y of 1~8 mole of %3+, the Y of preferably 2~6 moles %3+；And/or
The Ba of 28~38 moles of %2+, the Ba of more preferable 30~35 moles of %2+；And/or
The Sr of 5~12 moles of %2+, the Sr of preferably 5~10 moles %2+。
3. fluorphosphate glass according to claim 1 or 2, which is characterized in that the anion includes:
The F of 41~48 moles of %-, the F of preferably 42~46 moles %-；And/or
The O of 52~59 moles of %2-, the O of preferably 54~58 moles %2-。
4. fluorphosphate glass according to any one of claim 1-3, which is characterized in that n(Y 3++La 3+ )/
n(P 5+ +Al 3+ +Sr 2+ +Y 3+ )=0.075~0.5.
5. fluorphosphate glass described in any one of -4 according to claim 1, which is characterized in that the cation further wraps
It includes:
The Yb of 0~10 mole of %3+, the Yb of preferably 0~5 mole %3+；And/or
The Ca of 0~10 mole of %2+, the Ca of preferably 0~5 mole %2+；And/or
The Mg of 0~10 mole of %2+, the Mg of preferably 0~5 mole %2+。
6. fluorphosphate glass according to any one of claims 1-5, which is characterized in that n(Y 3+ +La 3+ )/n(Sr 2+ +Ba 2+ )
Greater than 0.11, preferably greater than 0.135, more preferable 0.14~0.65,
n(Sr 2++Y 3+ )/n(Al 3+ +Ba 2+ )=0.25~0.43, be free of endpoint 0.25, preferably 0.265~0.375, be free of endpoint
0.265。
7. fluorphosphate glass according to claim 1 to 6, which is characterized in that n(Y 3++Gd 3++Ba 2+ )/
n(P 5+ +Al 3+ +Sr 2++Ba 2+ )=0.435~0.505, preferably 0.44~0.5.
8. fluorphosphate glass described in any one of -7 according to claim 1, which is characterized in that n(sr 2++Ba 2+ )/
n(Y 3+ +Gd 3+ +La 3+ )=3.45~9, preferably 3.45~7.6, more preferable 3.55~5.55.
9. fluorphosphate glass according to claim 1 to 8, which is characterized in that the cation further wraps
It includes:
The Li of 0~15 mole of %+, the Li of preferably 0~10 mole %+；And/or
The Na of 0~15 mole of %+, the Na of preferably 0~10 mole %+；And/or
The K of 0~10 mole of %+, the K of preferably 0~5 mole %+；And/or
The B of 0~8 mole of %3+, the B of preferably 0~5 mole %3+；And/or
The Zn of 0~10 mole of %2+, the Zn of preferably 0~5 mole %2+；And/or
The In of 0~8 mole of %3+, the In of preferably 0~5 mole %3+；And/or
The Nb of 0~5 mole of %5+, the Nb of preferably 0~3 mole %5+；And/or
The Ti of 0~5 mole of %4+, the Ti of preferably 0~3 mole %4+；And/or
The Zr of 0~5 mole of %4+, the Zr of preferably 0~3 mole %4+；And/or
The Ta of 0~5 mole of %5+, the Ta of preferably 0~3 mole %5+；And/or
The Ge of 0~5 mole of %4+, the Ge of preferably 0~3 mole %4+。
10. fluorphosphate glass according to claim 1 to 9, which is characterized in that the fluorphosphate glass
Refractive index is 1.52~1.60, preferably 1.53~1.58, more preferable 1.55~1.58, and Abbe number is 68~75, preferably 69~74,
More preferable 70~73.
11. fluorphosphate glass according to claim 1 to 10, which is characterized in that the fluorphosphate glass
Thermal refractive index coefficient be -4.0 × 10-6/ degree Celsius hereinafter, it is preferred that -5.0 × 10-6/ degree Celsius hereinafter, more preferably -7.5 ×
10-6/ degree Celsius hereinafter, λ80No more than 370nm, preferably no greater than 360nm, more preferably no more than 350nm, λ5No more than 310nm,
Preferably no greater than 300nm, more preferably no more than 295nm.
12. fluorphosphate glass described in any one of -11 according to claim 1, which is characterized in that the fluorphosphate glass
Density be not higher than 4.7g/cm3, preferably no greater than 4.6g/cm3, more preferably no higher than 4.5g/cm3, stress optical coefficient is high
In 0.6 × 10-12/ Pa, preferably no greater than 0.5 × 10-12/ Pa, more preferably no higher than 0.4 × 10-12/ Pa, abrasion degree are not higher than
500, preferably no greater than 450, acidproof effect stability is not less than 2 grades, and preferably not less than 1 grade, water-fast effect stability is not less than 2
Grade, preferably not less than 1 grade.
13. a kind of gas preform, which is characterized in that the gas preform is using of any of claims 1-12
Fluorphosphate glass is made.
14. a kind of optical element, which is characterized in that the optical element uses fluorine phosphorus of any of claims 1-12
Gas preform described in silicate glass or claim 13 is made.
15. a kind of optical instrument, which is characterized in that the optical instrument has optical element described in claim 14.
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