CN111453989A - Lanthanide optical glass and glass preform, element and instrument thereof - Google Patents
Lanthanide optical glass and glass preform, element and instrument thereof Download PDFInfo
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- CN111453989A CN111453989A CN201910058932.4A CN201910058932A CN111453989A CN 111453989 A CN111453989 A CN 111453989A CN 201910058932 A CN201910058932 A CN 201910058932A CN 111453989 A CN111453989 A CN 111453989A
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- 239000011521 glass Substances 0.000 title claims abstract description 114
- 239000005304 optical glass Substances 0.000 title claims abstract description 38
- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 22
- 150000002602 lanthanoids Chemical class 0.000 title claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 17
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims description 38
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 9
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 101000840267 Homo sapiens Immunoglobulin lambda-like polypeptide 1 Proteins 0.000 claims description 2
- 102100029616 Immunoglobulin lambda-like polypeptide 1 Human genes 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000004031 devitrification Methods 0.000 abstract description 21
- 239000000126 substance Substances 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005457 optimization Methods 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000005499 meniscus Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 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
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- -1 oxide Chemical compound 0.000 description 1
- 238000005191 phase separation 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
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- 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
Abstract
The invention discloses lanthanide optical glass, and a prefabricated member, an element and an instrument thereof, which solve the problem that L a is overcome in the prior art2O3The influence on the properties such as refractive index, dispersion and crystallization upper limit temperature caused by the excessively high content of the glass needs to increase the production cost of the glass. The invention comprises the following components in percentage by weight: SiO 220～10％；B2O325～45％；La2O330～50％；Gd2O30～10％；Y2O33～20％；ZnO 0～10％；R20-8% of O. The invention can improve the refractive index/reduce the dispersion and reduce Gd simultaneously through reasonable optimization of the composition and the proportion2O3And Ta2O5The use amount of the glass reduces the cost, effectively improves the devitrification resistance and reduces the glassThe glass transition temperature ensures the excellence of the performance such as crystallization upper limit temperature, chemical stability and the like.
Description
Technical Field
The invention relates to the field of glass, in particular to lanthanide optical glass and a prefabricated member, an element and an instrument thereof.
Background
There is a rapid trend toward higher integration and functional improvement in recent devices using optical systems, and there is a growing desire to reduce the weight and size of optical systems. To fulfill this desire, optical designs using aspherical lenses made of high-performance glass are becoming mainstream. Generally, such a glass is heated to a temperature allowable for molding and then molded by precision press molding, thereby producing an aspherical lens. In particular, although a large aperture lens used recently is a spherical lens, in order to further enhance the function, it is becoming more commonLarge aperture aspherical lenses replace these lenses. There is an increasing need for high performance glasses for use in the production of these lenses to have high refractive index and low dispersion characteristics. It is considered that each of them contains B2O3And L a2O3The glass as a main component is a glass which has been used so far and satisfies these requirements and has high refractive index and low dispersion characteristics.
However, those glasses used so far have a problem that they generally have a high forming temperature. The high forming temperature causes the following problems:
the mold for high-precision mold pressing has the following performance requirements: can be processed with high surface accuracy and can be unchanged at the forming temperature. Therefore, the mold is generally made of a cemented carbide WC and is further coated with a metal as a separation film on the surface thereof for preventing the mold from adhering to the glass. However, even if the mold is coated with the separation film, resistance to repetition of cycles of the mold decreases with an increase in the molding temperature, and therefore, it is desirable to perform press molding at a lower temperature to ensure resistance to repetition of cycles of the mold.
In order to overcome the above-mentioned problems associated with high forming temperatures, various glasses known as optical glasses have been proposed in the prior art, which glasses comprise B as the main component2O3、La2O3And L i2However, each of these glasses is designed with an emphasis on chemical stability, resistance to thermal devitrification, and low pressure forming temperature characteristics, and is substantially free of more than 30% lanthanide elements, such as L a2O3. Thus, such glasses are susceptible to devitrification during high temperature forming processes, such as casting or billet forming.
La2O3The component is an essential component essential for increasing the refractive index of the glass and maintaining the light transmittance. It can be used to increase the Abbe number while increasing the refractive index of the glass. However, if the content is too large, for example, exceeds 38 wt%, the temperature coefficient of the relative refractive index tends to be large, the crystallization property tends to be deteriorated, and the chemical stability tends to be poor. Thus, in the prior art, it is known to,conventionally contains a high content of L a2O3In order to overcome the height L a2O3The content of the auxiliary oxide is usually added, as disclosed in CN201710970405.1, in a high-refractive index low-dispersion optical glass with excellent devitrification resistance, although high L a is adopted2O3But Gd is increased in order to lower the upper limit temperature of crystallization2O3And Ta2O5Due to Ta2O5At lower levels, it is generally desirable to increase Gd2O3Due to Gd2O3And Ta2O5Both are relatively expensive, and therefore, it is required to obtain a glass having a relatively high refractive index, an Abbe number and a crystallization upper limit temperature, and the cost thereof is relatively high.
Disclosure of Invention
The invention aims to provide lanthanide optical glass, which solves the problem of overcoming L a in the prior art2O3The influence on the properties such as refractive index, dispersion, crystallization upper limit temperature and the like caused by excessively high content needs to improve the production cost of the glass; through reasonable optimization of composition and proportion, Gd can be reduced while the refractive index is improved/the dispersion is reduced2O3And Ta2O5The usage amount of the composition reduces the cost, effectively improves the devitrification resistance, and ensures the excellence of the crystallization upper limit temperature, the chemical stability, the low softening point, easy mould pressing and other performances.
The invention is realized by the following technical scheme:
a lanthanide optical glass comprising, in wt%:
SiO20～10％；
B2O325～45％；
La2O330～50％；
Gd2O30～10％；
Y2O33～20％；
ZnO0～10％；
R2O0～8％；
R2o is L i2O、Na2O、K2One or more of O.
Further, comprises, in wt%:
SiO21-8%, preferably 2-6%; and/or
B2O328-40%, preferably 30-37%; and/or
La2O335-45%, preferably 38-43%; and/or
Gd2O30.5-8%, preferably 1-5%; and/or
Y2O35-18%, preferably 9-15%; and/or
ZnO1-8%, preferably 2-6%; and/or
R2O0.5 to 5%, preferably 0.5 to 3%;
R2o is L i2O、Na2O、K2One or more of O.
Further, the composition also comprises the following components in percentage by weight:
ZrO20-8%; and/or
Sb2O30 to 1 percent; and/or
RO0 to 5 percent; and/or
XO0 to 10 percent; and/or
TiO2+Nb2O5+WO30～5％；
Wherein, the RO is one or more of MgO, CaO, SrO and BaO; XO is Yb2O3、P2O5、GeO2、Ga2O3、SnO2One or more of (a).
Further, the composition also comprises the following components in wt percent:
ZrO20 to 5%, preferably 0 to 2%; and/or
Sb2O30 to 0.5%, preferably 0 to 0.1%; and/or
RO0 to 3%, preferably none; and/or
XO0 to 5 percent; and/or
TiO2+Nb2O5+WO30 to 3%, preferably none;
wherein, the RO is one or more of MgO, CaO, SrO and BaO; XO is Yb2O3、P2O5、GeO2、Ga2O3、SnO2One or more of (a).
Further, the ZnO and B2O3The ratio of (A) to (B) is 0-0.35; preferably 0.03 to 0.30; more preferably 0.05 to 0.20.
Further, the SiO2And B2O3The ratio of (A) to (B) is 0.02-0.35; preferably 0.05 to 0.30; more preferably 0.05 to 0.20.
Further, the L i2O and Gd2O3The ratio of (A) to (B) is more than 0.1; preferably 0.20 to 5.00; more preferably 0.30 to 2.00.
Further, the L i2O and Y2O3The ratio of (A) to (B) is 0.02-2.00; preferably 0.03 to 1.00; more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.25.
Further, Y2O3/(La2O3+B2O3) The value of (A) is 0.05 to 0.35; preferably 0.10 to 0.30; more preferably 0.14 to 0.25.
Further, Gd is2O3And L a2O3The ratio of (A) to (B) is 0.01-0.3; preferably 0.02 to 0.25; more preferably 0.03 to 0.20.
Further, Y2O3/(La2O3+Gd2O3) The value of (A) is 0.10 to 0.60; preferably 0.15 to 0.50; more preferably 0.2 to 0.40.
Further, does not contain Ta2O5And/or Al2O3。
Further, the upper limit crystallization temperature of the glass is 1100 ℃ or lower, preferably 1090 ℃ or lower, and more preferably 1080 ℃ or lower; the water-resistant stability of the glass is more than 2 types, preferably 1 type; the glass transition temperature is 630 ℃ or lower, preferably 620 ℃ or lower; the glass has a lambda 80 of 390nm or less, preferably 380nm or less, and more preferably 370nm or less; the glass has a lambda 5 of 300nm or less, preferably 290nm or less, and more preferably 280nm or less.
Further, the density of the glass was 4.50g/cm3Hereinafter, it is preferably 4.3g/cm3Hereinafter, more preferably 4.2g/cm3The following; the refractive index nd of the glass is 1.70-1.75, preferably 1.71-1.74, and more preferably 1.72-1.74; abbe number vd51 to 57, preferably 52 to 56, and more preferably 53 to 55.
The invention also includes glass preforms, optical elements, optical instruments. The glass prefabricated member is made of the optical glass, the optical element is made of the optical glass or the glass prefabricated member, and the optical instrument is made of the optical element.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention simultaneously increases L a on the basis of the technology of conventional dosage through the optimization of components and mixture ratio2O3、Y2O3Content of Gd is reduced2O3In conventional amounts, without using expensive Ta2O5The cost is effectively reduced;
2. the invention can also effectively ensure the excellence of the properties of low softening point, easy mould pressing, crystallization upper limit temperature, chemical stability and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
The composition ranges of the components of the optical glass of the present invention will be described below. In the present specification, the contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include endpoints, all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
In the present invention, B2O3The component is a network-forming body oxide forming the glass, and is a useful component for forming the glass skeleton.
B2O3Has the function of fluxing if B2O3If the content is too small, the devitrification resistance of the glass is not satisfactory, but if B is contained in the glass2O3If the content is too large, the refractive index is low, the chemical stability is poor, and the requirement is not satisfied. In the invention B2O3The content is set to be 25-45%, and preferably 28-40%; more preferably 30 to 37%.
La2O3The component (A) is an essential component essential for increasing the refractive index of the glass and maintaining the light transmittance, and is effective for increasing the Abbe number, if the content is too small, it is difficult to sufficiently obtain the above-mentioned effect, and if the content is too large, for example, exceeds 50%, the temperature coefficient with respect to the refractive index tends to become large, the crystallization property tends to deteriorate, and the chemical stability tends to be poor L a in the present invention2O3The content is set to be 30-50%, preferably 35-45%; more preferably 38 to 43%.
La2O3、Gd2O3、Y2O3And Yb2O3Among them, L a is the component having the greatest effect of increasing the refractive index of the glass and maintaining the stability of the glass2O3However, if only L a is used, the optical glass of the present invention2O3It is difficult to ensure sufficient glass stability, therefore, L a in the present invention2O3The component is introduced in the largest amount, and L a2O3And Y2O3Coexisting or preferably making L a2O3、Gd2O3And Y2O3Coexistence; however, in general, the more lanthanide oxides are introduced, the more the glass is prone to crystallization, and the difficulty is brought to mass production process manufacturing; thus Y in the invention2O3The content is set to be 3-20%, preferably 5-18%; more preferably 9-15%; gd (Gd)2O3The content is set to be 0-10%, preferably 0.5-8%; more preferably 1 to 5%.
SiO2Has the functions of adjusting the viscosity of the glass and the devitrification resistance if SiO2An excessive content of the component (B) may lower the meltability of the glass and increase the softening temperature, and if SiO is used2If the content is too small, the purpose of adjusting the viscosity of the glass and suppressing the tendency to crystallize may not be achieved. SiO in the invention2The content is set to 0-10%, preferably 1-8%, and more preferably 2-6%.
ZrO2When the amount of the component (A) is small, the glass devitrification temperature can be lowered to inhibit crystallization, and therefore, the chemical stability can be improved. If the content is too small, it is difficult to sufficiently obtain the above-mentioned effects, and if the content is too large, crystalline substances are likely to be generated in the glass. ZrO in the invention2The content is set to 0 to 8%, preferably 0 to 5%, and more preferably 0 to 2%.
The ZnO component is effective for lowering the devitrification temperature and lowering the Tg, but if the content thereof is too large, the chemical stability is liable to deteriorate. In the invention, the ZnO content is set to be 0-10%, preferably 1-8%, and more preferably 2-6%.
R2O includes L i2O、Na2O、K2O, the component having a temperature coefficient for decreasing the relative refractive index is largerThe effective components also have the effects of reducing the devitrification temperature and improving the chemical stability. If the content is too small, the effect described above is insufficient, and if the content is too large, the glass tends to exhibit an opacifying phenomenon, which is disadvantageous in removing glass streaks. In the invention, R2The content of O is set to 0 to 8%, preferably 0.5 to 5%, more preferably 0.5 to 3%, and further, when R is2O is preferably L i2The effects of increasing the meltability and lowering the Tg are more pronounced with O.
Sb2O3The component (B) has a defoaming effect in the glass melting step. Sb in the invention2O3The content is set to 0 to 1%, preferably 0 to 0.5%, and more preferably 0 to 0.1%.
The MgO component is an arbitrary component that lowers the melting temperature, but if the content thereof exceeds 5%, the stability against devitrification deteriorates, and the tendency to phase separation tends to increase. The CaO component is an optional component effective for lowering the devitrification temperature, lowering Tg and specific gravity, as in the ZnO component, but if the content thereof is too large, devitrification resistance is liable to deteriorate. The SrO component is an arbitrary component for lowering the devitrification temperature and adjusting the refractive index, but if the content thereof is too large, the devitrification resistance is liable to deteriorate. The BaO component is an optional component effective for lowering the devitrification temperature and adjusting the optical constant, but if the content thereof is too large, the devitrification resistance is liable to deteriorate. In the present invention, the RO content is set to 0 to 5%, preferably 0 to 3%, and more preferably not contained.
With appropriate introduction of a certain amount of TiO2、Nb2O5、WO3The total content is 0 to 5%, preferably 0 to 3%, and more preferably not contained, because the content of the glass dispersion increases when the content exceeds 5%, the glass dispersion increases, the glass coloring tendency increases, and the transmittance decreases.
Yb2O3Is an effective component for increasing the refractive index, but if the content is more than 10%, the melting temperature will be increased and the glass stability will be lowered. Thus, Yb of the invention2O3The content of (A) is 0 to 10%, preferably 0 to 5%, furtherPreferably not incorporated.
P2O5Can participate in the network structure to play a certain role, but when the introduction amount is more than 10 percent, the glass stability is reduced, the crystallization tendency is increased, and therefore, the P of the invention2O5The content of (b) is 0 to 10%, preferably 0 to 5%, and more preferably not introduced.
GeO2It is advantageous to lower the melting temperature of the glass and improve the glass stability, but in view of cost, it is preferable for those skilled in the art to use GeO in an amount as low as possible2Thus, GeO of the invention2The content of (b) is 0 to 10%, preferably 0 to 5%, and more preferably not introduced.
Ga2O3The glass stability can be suitably improved, but if the content is too high, Tg may be increased, and therefore, Ga in the present invention2O3The content of (b) is selected from 0 to 10%, preferably 0 to 5%, and more preferably not incorporated.
SnO2It may be added as a fining agent, but when the content exceeds 10%, the glass is colored, or when the glass is heated, softened, and subjected to secondary molding such as press molding, Sn becomes a starting point of nucleation, and tends to devitrify. Thus SnO2The content of (b) is 0 to 10%, preferably 0 to 5%, and more preferably no incorporation.
Other components not mentioned above, such as L u, can be added in small amounts as required within the range not impairing the characteristics of the glass of the present invention3+、Ce4+And the like. But V5+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Ag+And Mo6+The transition metal oxide component, if contained in a small amount alone or in combination, is preferably not substantially contained in the optical glass, which is required to have a transmittance at a wavelength in the visible light region, because the glass is colored and absorbs at a specific wavelength in the visible light region, thereby reducing the property of the present invention to improve the visible light transmittance.
In recent years, compounds of Pb, As, Th, Cd, Tl, Os, Be, and Se tend to Be used As harmful chemical substances under control, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
The term "not containing", "not introducing" or "0%" as used herein means that the compound, molecule or element is not intentionally added as a raw material to the glass of the present invention; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.
The invention simultaneously increases L a on the basis of the technology of conventional dosage through the optimization of components and mixture ratio2O3、Y2O3Content of Gd is reduced2O3In conventional amounts, and without the use of costly Ta2O5And the cost is effectively reduced. Meanwhile, the invention enables the components to be optimally matched by further adjusting the component proportion so as to improve the overall performance of the glass.
By convention Y in the present invention2O3/(La2O3+Gd2O3) Is effective against high L a2O3、Y2O3The defect caused by the content effectively improves the devitrification resistance, and can effectively ensure the excellence of the performance such as the crystallization upper limit temperature, the chemical stability and the like, and when the ratio exceeds 0.60, the crystallization upper limit temperature of the glass is increased, the chemical stability is deteriorated, and the coloring tendency is increased. Thus, Y2O3/(La2O3+Gd2O3) The value of (A) is set to 0.10 to 0.60, preferably 0.15 to 0.50; more preferably 0.2 to 0.40. Effects of the invention according to the embodimentsComparison with the comparative example is further verified.
In the present invention, ZnO and B are provided2O3Ratio of (ZnO/B)2O3Can further reduce the glass transition temperature Tg, increase the transmittance and reduce the degree of coloration, when ZnO/B is used2O3When the ratio exceeds 0.35, the devitrification resistance and chemical stability of the glass are rather deteriorated, and therefore, in some embodiments of the present invention containing ZnO, the ratio is set to 0 to 0.35, preferably 0.03 to 0.30, and more preferably 0.05 to 0.20.
By adjusting SiO2And B2O3The chemical stability and the stability of the finished glass can be effectively improved by the proportion of the components, and the effect is more obvious. When SiO is present2/B2O3When the ratio is less than 0.02 and exceeds 0.35, the glass forming stability of the glass is lowered and the chemical stability is lowered. Thus, some of the present invention contain SiO2In the embodiment (1), SiO2/B2O3The ratio is set to be 0.02-0.35, preferably 0.05-0.30, and more preferably 0.05-0.20.
In some cases containing L i2O and Gd2O3In the embodiment of (1), when L i2O and Gd2O3When the ratio of (A) to (B) is 0.1 or less, the devitrification resistance and chemical stability of the glass are lowered, therefore, L i in the present invention2O and Gd2O3The ratio of (A) to (B) is set to 0.1 or more, preferably 0.20 to 5.00, more preferably 0.30 to 2.00. Through the setting of the conditions, the glass transition temperature can be effectively reduced, simultaneously, the glass transmittance is effectively improved, the degree of coloration is reduced, and the lambda value of the glass is adjusted80Controlled below 390nm, lambda5Controlled below 300 nm.
In some cases containing L i2O and Y2O3In the embodiment (2), the L i2O and Y2O3Ratio of L i2O/Y2O30.02 to 2.00, preferably 0.03 to 1.00, more preferably 0.05 to 0.50, most preferably 0.05 to 0.25, vain L i2O/Y2O3When the glass transition temperature is lower than 0.02, the glass specific gravity is increasedIncrease when L i2O/Y2O3Above 2.0, the glass cost increases and the devitrification resistance of the glass deteriorates, so that the glass transition temperature can be effectively lowered and the density can be effectively lowered by the setting of the above range.
To achieve excellent optical performance, Y is optimized2O3/(La2O3+B2O3) When the ratio of (b) exceeds 0.35, the crystallization upper limit temperature of the glass becomes high, the chemical stability becomes poor, and the coloring tendency becomes high. Thus, Y is2O3/(La2O3+B2O3) The ratio of (A) to (B) is set to 0.05 to 0.35, preferably 0.10 to 0.30, and more preferably 0.14 to 0.25.
In the present invention, Gd is2O3And L a2O3The ratio of (A) to (B) is adjusted within the range of 0.01-0.30, so that the crystallization upper limit temperature of the glass is not increased, the glass forming property is better, glass bubbles are not easy to generate in the melting process, and good optical performance, forming performance and the like are also ensured. When the ratio exceeds 0.3, the refractive index is increased to some extent, but the cost is increased and the crystallization upper limit temperature is increased, so that Gd is preferable in the present invention2O3/La2O30.02 to 0.25; more preferably, Gd2O3/La2O30.03 to 0.20.
Examples
The specific compositions and proportions of the lanthanide optical glasses in wt% are shown in tables 1-4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
In order to obtain glasses having compositions shown in tables 1 to 4, raw materials (carbonate, nitrate, hydroxide, oxide, boric acid, etc.) corresponding to optical glass components are weighed in proportion, mixed sufficiently to obtain a blended raw material, the blended raw material is put into a platinum crucible, heated to 1200 to 1400 ℃, melted, stirred, clarified to form uniform molten glass, the molten glass is appropriately cooled, poured into a preheated mold, kept at 550 to 750 ℃ for 2 to 4 hours, and then slowly cooled to obtain the optical glass. The characteristics of each glass were measured for the glass products produced in the above examples by the following measurement methods, and the measurement results are shown in tables 5 to 8. Wherein each measurement method is as follows:
density (ρ): testing according to GB/T7962.20-2010.
Refractive index (nd) and abbe number (vd): testing according to GB/T7962.1-2010.
Transition temperature (Tg): testing according to GB/T7962.16-2010.
Coloring of glass:
coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention80/λ5) And (4) showing. Lambda [ alpha ]80Refers to the wavelength, lambda, corresponding to a glass having a transmittance of 80%5It means a wavelength corresponding to a glass transmittance of 5%, wherein λ 80 is measured using a glass having a thickness of 10 ± 0.1mm with two opposite planes parallel to each other and optically polished, and a wavelength at which a spectral transmittance in a wavelength region from 280nm to 700nm is measured and a transmittance of 80% is exhibited. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glassinLight transmitted through the glass and having an intensity I emitted from a planeoutIn the case of light of (1) through (I)out/IinThe quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss.
The spectral transmittance was measured using a glass sample having a thickness of 10. + -. 0.1mm with two optically polished planes opposed to each other, and calculated from the result thereof.
Upper limit temperature of crystallization:
measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1200 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.
Stability to Water action (powder method) DW: test method according to GB/T17129.
The test results of this example are shown in tables 5 to 8.
TABLE 5
TABLE 6
TABLE 7
TABLE 8
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
The glass preform, the optical element and the optical instrument of the present invention are described as follows:
the glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention.
The glass preform of the present invention is made of the optical glass of the present invention, has a high refractive index and low dispersion characteristics, and is useful in various optical elements and optical designs. In particular, it is preferable to manufacture optical elements such as lenses, prisms, and mirrors from the glass of the present invention by means of precision press molding or the like. It should be noted that the features and advantages described above for glass apply equally to the glass preform and are not described in detail here.
The optical element of the present invention is made using the glass or glass preform of the present invention. Thus, the optical element of the present invention has high-refraction low-dispersion characteristics, and can provide various optical elements such as lenses and prisms having excellent performance. For example, the optical element of the present invention may be a spherical lens, an aspherical lens, various lenses such as a microlens, a diffraction grating, a lens with a diffraction grating, a lens array, a prism, or the like. In addition, an optical thin film such as an antireflection film, a total reflection film, a partial reflection film, or a film having spectroscopic characteristics may be provided on the optical element as necessary. When the optical element is a lens, the lens includes, but is not limited to, various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface. Further, since the prism has a relatively high refractive index, by combining the prism with an imaging optical system and bending the optical path to direct the prism in a desired direction, a compact and wide-angle optical system can be realized.
It should be noted that the features and advantages described above for glass and glass preforms apply equally to the optical element and are not described in detail here.
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like. By using the optical element having excellent performance in the optical instrument, the customer experience of the optical instrument can be improved. It should be noted that the features and advantages described above for the optical element apply equally to the optical instrument and are not described in detail here.
Claims (17)
1. Lanthanide optical glass, characterized in that it comprises, in wt.%:
R2o is L i2O、Na2O、K2One or more of O.
2. The lanthanide optical glass as defined in claim 1, comprising, in wt%:
R2o is L i2O、Na2O、K2One or more of O.
3. The lanthanide optical glass of claim 1, further comprising, in wt%:
wherein, the RO is one or more of MgO, CaO, SrO and BaO; XO is Yb2O3、P2O5、GeO2、Ga2O3、SnO2One or more of (a).
4. The lanthanide optical glass of claim 1, further comprising, in wt%:
wherein, the RO is one or more of MgO, CaO, SrO and BaO; XO is Yb2O3、P2O5、GeO2、Ga2O3、SnO2One or more of (a).
5. The lanthanide optical glass as in any one of claims 1-4, wherein said ZnO and B are2O3The ratio of (A) to (B) is 0-0.35; preferably 0.03 to 0.30; more preferably 0.05 to 0.20.
6. The lanthanide optical glass as in any one of claims 1-4, wherein said SiO is2And B2O3The ratio of (A) to (B) is 0.02-0.35; preferably 0.05 to 0.30; more preferably 0.05 to 0.20.
7. The lanthanide optical glass as in any one of claims 1-4, wherein said L i is2O and Gd2O3The ratio of (A) to (B) is more than 0.1; preferably 0.20 to 5.00; more preferably 0.30 to 2.00.
8. The lanthanide optical glass as in any one of claims 1-4, wherein said L i is2O and Y2O3The ratio of (A) to (B) is 0.02-2.00; preferably 0.03 to 1.00; more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.25.
9. The lanthanide optical glass as in any one of claims 1-4, wherein Y is2O3/(La2O3+B2O3) The value of (A) is 0.05 to 0.35; preferably 0.10 to 0.30; more preferably 0.14 to 0.25.
10. The lanthanide optical glass of any of claims 1-4, wherein said Gd2O3And L a2O3The ratio of (A) to (B) is 0.01-0.3; preferably 0.02 to 0.25; more preferably 0.03 to 0.20.
11. The lanthanide optical glass as in any one of claims 1-4, wherein Y is2O3/(La2O3+Gd2O3) The value of (A) is 0.10 to 0.60; preferably 0.15 to 0.50; more preferably 0.2 to 0.40.
12. The lanthanide optical glass as in any one of claims 1-4, not including Ta2O5And/or Al2O3。
13. The lanthanide optical glass as defined in any one of claims 1 to 4, wherein the glass has an upper crystallization temperature of 1100 ℃ or lower, preferably 1090 ℃ or lower, and more preferably 1080 ℃ or lower; the water-resistant stability of the glass is more than 2 types, preferably 1 type; the glass transition temperature is 630 ℃ or lower, preferably 620 ℃ or lower; the glass has a lambda 80 of 390nm or less, preferably 380nm or less, and more preferably 370nm or less; the glass has a lambda 5 of 300nm or less, preferably 290nm or less, and more preferably 280nm or less.
14. The lanthanide optical glass as in any one of claims 1-4, wherein the density of the glass is 4.50g/cm3Hereinafter, it is preferably 4.3g/cm3Hereinafter, more preferably 4.2g/cm3The following; the refractive index nd of the glass is 1.70-1.75, preferably 1.71-1.74, and more preferably 1.72-1.74; abbe number vd51 to 57, preferably 52 to 56, and more preferably 53 to 55.
15. A glass preform made of the optical glass according to any one of claims 1 to 14.
16. An optical element produced from the optical glass according to any one of claims 1 to 14 or the glass preform according to claim 15.
17. An optical device fabricated using the optical element of claim 16.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115925254A (en) * | 2022-05-30 | 2023-04-07 | 盐城晶鑫光学科技有限公司 | High-refractive-index lanthanide optical glass and preparation method thereof |
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