CN110156325A - 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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- CN110156325A CN110156325A CN201910473404.5A CN201910473404A CN110156325A CN 110156325 A CN110156325 A CN 110156325A CN 201910473404 A CN201910473404 A CN 201910473404A CN 110156325 A CN110156325 A CN 110156325A
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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 of 25~40 moles of %5+；The Al of 8~22 moles of %3+；The Ln of 1~30 mole of %3+, Ln3+For La3+、Gd3+、Y3+And Yb3+At least one of；The R of 25~55 moles of %2+, R2+For Ba2+、Ca2+、Sr2+And Mg2+At least one of；The anion includes: the F of 38~50 moles of %‑；The O of 50~62 moles of %2‑, wherein nLn 3+/nR 2+Greater than 0.11.For the refractive index of the fluorphosphate glass 1.52~1.60, Abbe number is not less than 68, and has excellent optical property etc., while having lower refractive index high temperature coefficient, to be suitable for outdoor high temperature environment, meets market needs.
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,
Be produce the better optical material of advanced digital product, therefore its with very high demand, especially refractive index nd 1.52~
1.60, the colourless fluorphosphate glass of low dispersion of the Abbe number vd not less than 68, while existing optical glass is in application process
In its refractive index varied widely with temperature caused by heat difference, to hot environment especially outdoor high temperature environment work
Instrument precision and accuracy all have larger impact.
Therefore, it is necessary to develop low dispersion and be suitable for the colourless fluorophosphate optical glass of outdoor high temperature environment.
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 meets market needs to be suitable for outdoor high temperature environment.
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 Ln of 1~30 mole of %3+, Ln3+For La3+、Gd3+、Y3+And Yb3+At least one of；25~55 moles of %'s
R2+, R2+For Ba2+、Ca2+、Sr2+And Mg2+At least one of；The anion includes: the F of 38~50 moles of %-；50~62 rub
The O of your %2-, wherein nLn 3+/nR 2+Greater than 0.11.
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, to be suitable for outdoor high temperature environment, 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 Ln of 2~20 moles of %3+, the Ln of preferably 3~15 moles %3+；And/or the R of 30~50 moles of %2+, preferably 35-45 rubs
The R of your %2+.Thus, it is possible to guarantee that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, Ln described in above-mentioned fluorphosphate glass composition3+It include: 0~8 mole of %
La3+, the La of preferably 0~5 mole %3+, be free of endpoint 0, the La of more preferable 0.5~4 mole of %3+；And/or 1~10 mole of %
Gd3+, the Gd of preferably 1~6 mole %3+, the Gd of more preferable 1~5 mole of %3+；And/or the Y of 1~10 mole of %3+, preferably 1~8
The Y of mole %3+, 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+.By
This, it is ensured that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, R described in above-mentioned fluorphosphate glass composition2+It include: 25~40 moles of %
Ba2+, the Ba of preferably 28~38 moles %2+, the Ba of more preferable 30~35 moles of %2+；And/or the Ca of 0~10 mole of %2+, excellent
Select the Ca of 0~5 mole of %2+；And/or the Sr of 3~15 moles of %2+, the Sr of preferably 5~12 moles %2+, more preferable 5~10 rub
The Sr of your %2+；And/or the Mg of 0~10 mole of %2+, the Mg of preferably 0~5 mole %2+.Thus, it is possible to guarantee the fluorophosphate
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, nLn 3+/nR 2+Greater than 0.135, preferably
0.14~0.65.Thus, it is possible to guarantee that the fluorphosphate glass has excellent performance.
In some embodiments of the invention, the Ln3+For Y3+And/or La3+, the R2+For Sr2+And/or Ba2+.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(Sr 2++Y 3+ )/n(Al 3+ +Ba 2+ )It is 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 the fluorophosphate glass
Glass has excellent performance.
In some embodiments of the invention, in above-mentioned fluorphosphate glass composition, n(Gd 3++La 3+ )/n(Y 3+ +Ba 2+ )It is greater than
0.085, preferably greater than 0.11, more preferable 0.115~0.165.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+ )/n(P 5+ +Al 3+ +Sr 2+ +Ba 2+ )
Less than 0.12, preferably 0.075~0.115.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 thermal refractive index coefficient of above-mentioned fluorphosphate glass is -4.0 × 10-6/ take the photograph
Family name's degree is hereinafter, it is preferred that -5.0 × 10-6/ degree Celsius hereinafter, more preferably -7.5 × 10-6/ degree Celsius hereinafter, 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 some embodiments of the invention, the transition temperature of above-mentioned fluorphosphate glass is not higher than 510 degrees Celsius, preferably
Not higher than 500 degrees Celsius, more preferably no higher than 495 degrees Celsius, λ80No more than 370nm, preferably no greater than 360nm, more preferably not
Greater than 350nm, λ5No more than 310nm, preferably no greater than 300nm, more preferably no more than 295nm, abrasion degree is excellent not higher than 500
Choosing is not higher than 450.
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 Ln of 1~30 mole of %3+, Ln3+For La3+、Gd3+、Y3+And Yb3+At least one of；The R of 25~55 moles of %2+, R2+
For Ba2+、Ca2+、Sr2+And Mg2+At least one of；The anion includes: the F of 38~50 moles of %-；50~62 moles of %'s
O2-, wherein nLn 3+/nR 2+Greater than 0.11.It should be noted that in cation component molar % be the cation and it is all it is positive from
The ratio of sub- total mole number, similarly in anion component molar % be the anion and all anion total mole numbers ratio.
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 lower dispersion, lower
Thermal refractive index coefficient and excellent water-fast acidproof effect stability etc., and present inventor passes through numerous studies
It was found that passing through Ln in control glass ingredient3+(it is selected from La3+、Gd3+、Y3+And Yb3+At least one of) molal quantity and R2+(choosing
From Ba2+、Ca2+、Sr2+And Mg2+At least one of) the ratio between molal quantity nLn 3+/nR 2+Greater than 0.11, collaboration is played between each component
Effect, can be improved glass refractive index and acidproof water-fast effect stability, and reduce dispersion and thermal refractive index coefficient, make
The glass be suitable for outdoor high temperature environment, obtained fluorphosphate glass refractive index be 1.52~1.60, Abbe number be 68~
75, thermal refractive index coefficient is -4.0 × 10-6/ degree Celsius hereinafter, acidproof effect stability is not less than 2 grades, water-fast effect stabilization
Property be not less than 2 grades, further preferably control glass ingredient in Ln3+Molal quantity and R2+The ratio between molal quantity nLn 3+/nR 2+Greater than 0.135,
Gained fluorphosphate glass refractive index is 1.53~1.58, and Abbe number is 69~74, and thermal refractive index coefficient is -5.0 × 10-6/
Degree Celsius hereinafter, acidproof effect stability is not less than 1 grade, water-fast effect stability more preferably can control glass group not less than 1 grade
Ln in point3+Molal quantity and R2+The ratio between molal quantity nLn 3+/nR 2+It is 0.14~0.65, gained fluorphosphate glass refractive index is 1.55
~1.58, Abbe number is 70~73, and thermal refractive index coefficient is -7.5 × 10-6/ degree Celsius or less.Further, preferably Ln3+
For Y3+And/or La3+, more preferable Ln3+For Y3+And La3+Summation, preferably R2+For Sr2+And/or Ba2+, more preferable R2+For Sr2+And Ba2 +Summation, gained fluorphosphate glass have excellent optical property and lower thermal refractive index coefficient.
Inventor also found simultaneously, and the fluorphosphate glass of the application requires excellent special at glass stability and optics
Property and lower abrasion degree, and the present inventor by numerous studies find, pass through control glass ingredient in Sr2+And Y3 +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, without end
Point 0.25 acts synergistically between each component, can be improved glass at glass stability and optical property, and reduce wear intensity,
To improve the machinability of glass, the abrasion degree of obtained fluorphosphate glass is not higher than 500, λ80No more than 370nm, λ5No
Greater than 310nm, Sr in glass ingredient is more preferably controlled2+And Y3+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 0.265~0.375, endpoint 0.265 is free of, so that the abrasion degree of gained fluorphosphate glass
Not higher than 450, λ80No more than 360nm, preferably no greater than 350nm, λ5No more than 300nm, preferably no greater than 295nm.
Further, inventor also found, pass through Gd in control glass ingredient2+And La3+Total molal quantity and Y3+With
Ba2+The ratio between total molal quantity (n(Gd 3++La 3+ )/n(Y 3+ +Ba 2+ )) be greater than 0.085, can be further improved glass at glass stability
And optical characteristics, and transition temperature is considerably lower, to be easy to be molded, small to grinding tool damage, ensure that mold uses the longevity
Life, the transition temperature of obtained fluorphosphate glass are not higher than 510 degrees Celsius, further preferably control Gd in glass ingredient2+With
La3+Total molal quantity and Y3+And Ba2+The ratio between total molal quantity (n(Gd 3++La 3+ )/n(Y 3+ +Ba 2+ )) it is greater than 0.11, obtained fluorine phosphorus
The transition temperature of silicate glass is not higher than 500 degrees Celsius, still more preferably Gd in control glass ingredient2+And La3+Total rub
That number and Y3+And Ba2+The ratio between total molal quantity (n(Gd 3++La 3+ )/n(Y 3+ +Ba 2+ )) it is 0.115~0.165, obtained fluorophosphate
The transition temperature of glass is not higher than 495 degrees Celsius.
Further, inventor also found, pass through Y in control glass ingredient3+And Gd3+Total molal quantity and P5+、Al3+、
Sr2+And Ba2+The ratio between total molal quantity (n(Y 3++Gd 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Ba 2+ )) it is greater than 0.12, it can further be more advantageous to tune
Whole glass refraction guarantees dispersion, and good at glass stability, and transition temperature is lower, preferably Y in control glass ingredient3+
And Gd3+Total molal quantity and P5+、Al3+、Sr2+And Ba2+The ratio between total molal quantity (n(Y 3++Gd 3+ )/n(P 5+ +Al 3+ +Sr 2+ +Ba 2+ )) be
0.075~0.115.
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, transition temperature Tg
Fluorphosphate glass gradually can become mouldable state by solid-state in a certain temperature range.Transition temperature TgRefer to that glass tries
Sample is from room temperature to the temperature T that hangs down that speedss, low-temperature region and high-temperature area straight line portion extended line intersection intersection point corresponding to
Temperature.Transition temperature TgIt is measured by method as defined in GB/T7962.16-2010.
Transition temperature (the T of glass of the present inventiong) 510 DEG C are not higher than, preferably no greater than 500 DEG C, more preferably no higher than 495
℃。
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.
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, to be suitable for outdoor high temperature environment, set in various optical elements and optics
It is useful on meter.It is particularly preferred to be made by fluorphosphate glass of the invention using means such as precision press moldings
Make the optical elements such as camera lens, prism, reflecting mirror.It should be noted that it is above-mentioned for feature described in fluorphosphate glass and
Advantage is equally applicable to the gas preform, and details are not described herein again.
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, to be suitable for outdoor high temperature environment, it is excellent to be capable of providing performance
The optical elements such as different various lens, prism.For example, optical element of the invention can be spherical lens, non-spherical lens, micro-
The various lens such as lens, diffraction grating, the lens with diffraction grating, lens array, prism etc..In addition, when necessary can be in the light
It learns and the optical thin films such as antireflection film, total reflection film, part reflectance coating, film with dichroism is set on element.It needs to illustrate
, it is above-mentioned to be equally applicable to the optical element for feature and advantage described in fluorphosphate glass and gas preform,
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 4 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 4.
Table 1
Table 2
Table 3
Table 4
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 (18)
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 Ln of 1~30 mole of %3+, Ln3+For La3+、Gd3+、Y3+And Yb3+At least one of；
The R of 25~55 moles of %2+, R2+For Ba2+、Ca2+、Sr2+And Mg2+At least one of；
The anion includes:
The F of 38~50 moles of %-；
The O of 50~62 moles of %2-,
Wherein, nLn 3+/nR 2+Greater than 0.11.
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 Ln of 2~20 moles of %3+, the Ln of preferably 3~15 moles %3+；And/or
The R of 30~50 moles of %2+, the R of preferably 35-45 moles %2+。
3. fluorphosphate glass according to claim 1 or 2, which is characterized in that the Ln3+Include:
The La of 0~8 mole of %3+, the La of preferably 0~5 mole %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+, the Gd of preferably 1~6 mole %3+, the Gd of more preferable 1~5 mole of %3+；And/or
The Y of 1~10 mole of %3+, the Y of preferably 1~8 mole %3+, 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+。
4. fluorphosphate glass according to any one of claim 1-3, which is characterized in that the R2+Include:
The Ba of 25~40 moles of %2+, the Ba of preferably 28~38 moles %2+, 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+；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+；And/or
The Mg of 0~10 mole of %2+, the Mg of preferably 0~5 mole %2+。
5. fluorphosphate glass described in any one of -4 according to claim 1, 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-。
6. fluorphosphate glass according to any one of claims 1-5, which is characterized in that nLn 3+/nR 2+Greater than 0.135,
It is preferred that 0.14~0.65.
7. fluorphosphate glass according to claim 1 to 6, which is characterized in that the Ln3+For Y3+And/or
La3+, the R2+For Sr2+And/or Ba2+。
8. fluorphosphate glass described in any one of -7 according to claim 1, which is characterized in that n(Sr 2++Y 3+ )/n(Al 3+ +Ba 2+ )
Be 0.25~0.43, be free of endpoint 0.25, preferably 0.265~0.375, be free of endpoint 0.265.
9. fluorphosphate glass according to claim 1 to 8, which is characterized in that n(Gd 3++La 3+ )/n(Y 3+ +Ba 2+ )
Greater than 0.085, preferably greater than 0.11, more preferable 0.115~0.165.
10. fluorphosphate glass according to claim 1 to 9, which is characterized in that n(Y 3++Gd 3+ )/
n(P 5+ +Al 3+ +Sr 2+ +Ba 2+ )Less than 0.12, preferably 0.075~0.115.
11. fluorphosphate glass according to claim 1 to 10, 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.
12. fluorphosphate glass described in any one of -11 according to claim 1, which is characterized in that the cation is further
Include:
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+。
13. fluorphosphate glass described in any one of -12 according to claim 1, 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.
14. fluorphosphate glass according to claim 1 to 13, 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, acidproof effect stability is not less than 2 grades, preferably not less than 1 grade, water-fast effect stability not less than 2 grades,
Preferably not less than 1 grade.
15. fluorphosphate glass described in any one of -14 according to claim 1, which is characterized in that the fluorphosphate glass
Transition temperature be not higher than 510 degrees Celsius, preferably no greater than 500 degrees Celsius, more preferably no higher than 495 degrees Celsius, λ80It is not 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, abrasion degree is not higher than 500, preferably no greater than 450.
16. a kind of gas preform, which is characterized in that the gas preform is using described in any one of claim 1-15
Fluorphosphate glass is made.
17. a kind of optical element, which is characterized in that the optical element is using fluorine phosphorus described in any one of claim 1-15
Gas preform described in silicate glass or claim 16 is made.
18. a kind of optical instrument, which is characterized in that the optical instrument has optical element described in claim 17.
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