CN108558202B - Optical glass with high refractive index - Google Patents

Optical glass with high refractive index Download PDF

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CN108558202B
CN108558202B CN201810846673.7A CN201810846673A CN108558202B CN 108558202 B CN108558202 B CN 108558202B CN 201810846673 A CN201810846673 A CN 201810846673A CN 108558202 B CN108558202 B CN 108558202B
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glass
optical glass
refractive index
high refractive
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CN108558202A (en
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欧阳胜明
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WANGJIANG TIANCHANG OPTICAL INSTRUMENTS Co.,Ltd.
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Wangjiang Tianchang Optical Instruments Co ltd
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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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses an optical glass, which is composed of a glass substrate,the composition is expressed by weight percentage and comprises: SiO 22：5‑15％、B2O3：10‑30％、La2O3：18‑30％、Nb2O5：5‑15％、Gd2O3：4‑20％、Bi2O3：2‑8％、TiO21‑8％、ZrO2：3‑12％、Ta2O5：2‑10％、CaO：1‑10％、Sb2O3: 0 to 0.2 percent; wherein said Bi2O3For doping with Zn2+Of Bi2O3. The optical glass provided by the invention is prepared by adding Bi into2O3Is doped with Zn2+The use of ZnO, which is highly aggressive to the melting apparatus, is avoided, while the contribution of ZnO to obtaining high-quality optical glass is retained.

Description

Optical glass with high refractive index
Technical Field
The invention relates to the technical field of optical materials, in particular to optical glass with high refractive index.
Background
Optical glass is a glass material used for manufacturing lenses, prisms, mirrors, windows, and the like in optical instruments or mechanical systems. The optical glass has good light transmission performance and high refractive index, and is widely applied to manufacturing optical instruments such as spectacle lenses, cameras, telescopes, microscopes, lenses and the like. With the advancement of science and technology, digital products are updated, the demand of optical glass is more and more, and higher requirements are also put forward on the performance of the optical glass.
Chinese patent application CN1772671A discloses an optical glass with a refractive index of 1.65-1.74 and an Abbe number of 36-45. The components of the material contain 8-30 wt% of ZnO and 5-26 wt% of BaO. Because of the high content of ZnO and BaO, the glass has strong erosion to a smelting device in the melting process of glass raw materials, the glass with excellent internal quality is difficult to be smelted, and the introduction of BaO influences the density of the glass.
Chinese patent application CN101229955A discloses an optical glass with a refractive index of 1.69-1.74 and an abbe number of 40-45, which contains 26-40 wt% of ZnO. Because the ZnO content is high, the corrosion to a smelting device is strong in the melting process of glass raw materials, and the glass with excellent internal quality is difficult to be smelted.
Chinese patent application CN102241479A discloses an optical glass with a refractive index of 1.75-1.95 and an abbe number of 30-40, which contains 5-20 wt% of ZnO. Because the ZnO content is high, the corrosion to a smelting device is strong in the melting process of glass raw materials, and the glass with excellent internal quality is difficult to be smelted.
From the above, it is known that too much ZnO deteriorates the devitrification resistance and chemical stability of the glass. However, ZnO is an important component for forming low-melting optical glass, and the abandonment of ZnO is also a loss for obtaining high-quality optical glass.
Disclosure of Invention
Based on the problems in the background art, the present invention provides an optical glass with high refractive index, which is prepared by adding Bi to2O3Is doped with Zn2+The use of ZnO, which is highly aggressive to the melting apparatus, is avoided, while the contribution of ZnO to obtaining high-quality optical glass is retained.
The invention provides high-refractive-index optical glass, which comprises the following components in percentage by weight: SiO 22：5-15％、B2O3：10-30％、La2O3：18-30％、Nb2O5：5-15％、Gd2O3：4-20％、Bi2O3：2-8％、TiO21-8％、ZrO2：3-12％、Ta2O5：2-10％、CaO：1-10％、Sb2O3: 0 to 0.2 percent; wherein said Bi2O3For doping with Zn2+Of Bi2O3。
Preferably, the optical glass further comprises Y2O3：1-10％。
Preferably, 0.3 ≦ SiO in weight percent2/B2O3≤1.2。
Preferably, 1.5 percent or more of La is calculated by weight percentage2O3/SiO2≤4。
Preferably, 0.4 percent or less of La is calculated by weight percentage2O3/(La2O3+Nb2O5+Gd2O3)≤0.6。
Preferably, the weight percentage of Bi is more than or equal to 8 percent2O3+TiO2+ZrO2≤20％。
Preferably, the Bi2O3Middle Zn2+The doping content of (A) is 5-10 wt%.
Preferably, the Bi is prepared2O3Method bagComprises the following steps: dissolving bismuth nitrate in ethylene glycol, adding zinc salt, mixing uniformly, then sending into a microwave reactor for microwave heating treatment, performing microwave heating 5-8 times by adopting microwave with power of 300-600W, heating for 2-6min each time, cooling, washing with water and absolute ethyl alcohol respectively after filtering, roasting for 1-2h at 500-600 ℃ after drying to obtain the Zn-doped alloy2+Of Bi2O3。
Preferably, the density of the optical glass is lower than 3.50g/cm3The glass transition temperature is 600 ℃ or lower.
The invention has the beneficial effects that the invention does not contain ZnO which has strong erosion to a smelting device, and Bi is used for dissolving the ZnO2O3Is doped with Zn2+Can reduce the melting point of the optical glass while reducing the erosion effect on a smelting device in the glass production process, and adopts Bi2O3The glass has improved stability, high refractive index and high dispersion, and the glass transition point (Tg) is reduced, so the glass is an indispensable component for realizing the purpose of the invention; with a suitable amount of Ta2O5、Gd2O3、Y2O3So that the optical glass has lower density and excellent devitrification resistance; controlling SiO in a formulation2/B2O3The molding viscosity of the glass is increased. Finally, by optimizing the proportion of each component, the transmittance and the product quality of the optical glass are improved, the corrosion of a smelting device in the smelting process is reduced, the manufacturing cost of the optical glass is reduced, and the excellent high-refraction low-dispersion optical glass can be obtained.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
In the optical glass of the present invention, each component is selected in the above-mentioned content for the reasons described below. As described below, the contents of the respective components are expressed in weight percent (wt%).
SiO2Is a glass network generation body, is a framework of optical glass, and has the functions of improving the chemical stability of the glass and maintaining the anti-devitrification performance of the glassAct to thereby control SiO2Is 5% or more, and SiO is too low2The content of the crystal growth inhibitor reduces the content of the bridge oxygen in the glass, the crystallization upper limit temperature of the glass exceeds 1100 ℃, and the light transmission performance of the glass is deteriorated, but the content of the crystal growth inhibitor exceeds 15 percent by weight, the glass becomes very refractory, the refractive index required by the invention cannot be obtained, and the Nb content is reduced2O5Meltability in glass, therefore SiO2The weight percentage is preferably in the range of 5-15%.
B2O3Is a glass network former, especially in high-refractive low-dispersion lanthanide glasses, B2O3Is an essential component for obtaining devitrification stable glass. When B is present2O3When the content is less than 10%, the crystallization stability of the glass is not ideal enough; but when B is2O3When the content is more than 30%, the chemical stability of the glass may be lowered. Thus, B2O3The content is limited to 10-30%.
By adjusting SiO2/B2O3The ratio of (A) to (B) can play a role in adjusting the viscosity of the glass. The viscosity of the glass is an important basis for setting the production process, and the setting of the clarifying temperature, the forming temperature and the heat treatment temperature of the glass depends on the viscosity of the glass. Therefore, the proper glass viscosity can effectively reduce the production difficulty of the glass. When SiO is present2/B2O3The glass has a suitable viscosity when the ratio of (A) to (B) is in the range of 0.3 to 1.2.
La2O3The optical fiber is an essential component for obtaining the high-refraction low-dispersion characteristic required by the invention, and if the content of the component is less than 18 percent, the optical constant is difficult to meet the design requirement; when the content is more than 30%, the devitrification resistance of the glass is remarkably deteriorated. Thus, the La of the present invention2O3The content of (A) is 18-30%.
Nb2O5The optical glass of the present invention has the effects of increasing the refractive index of the optical glass, improving chemical stability and devitrification performance, and is an essential component of the optical glass of the present invention. In the present invention, when the content is less than 5% by weight, the optical properties expected in the present invention are not achieved,however, when the content exceeds 15% by weight, the devitrification property of the glass gradually deteriorates and the optical properties expected in the present invention are not obtained. The weight percentage of the components is preferably controlled as follows: 5-15%.
Gd2O3Is helpful for increasing refractive index and reducing dispersion when Gd2O3When the content is less than 4%, the above effects are not obvious; however, if the content is more than 20%, the devitrification resistance and chemical stability of the glass are deteriorated. Thus, in the present invention, Gd2O3The content of (A) is 4-20%.
The component with high refraction and low dispersion of the invention also introduces Y2O3The melting property and the devitrification resistance of the glass are improved, the upper limit crystallization temperature of the glass can be reduced, and if the content of the glass is less than 1%, the effect is not obvious; however, if the content exceeds 10%, the stability and devitrification resistance of the glass are lowered. Thus, Y2O3The content range is 1-10%.
La2O3、Nb2O5、Gd2O3Can play a role in increasing the refractive index and reducing the dispersion when only La is used2O3、Nb2O5、Gd2O3When the amount is within the above range, the devitrification resistance of the glass is not stable. Therefore, the optical glass of the present invention is La2O3And La2O3、Nb2O5、Gd2O3The ratio of the total content is in the range of 0.4 to 0.6, and when the ratio is out of the above range, the thermal stability of the glass is deteriorated and the devitrification resistance is lowered.
Bi2O3The glass has improved stability, high refractive index and high dispersion, and the glass transition point (Tg) is reduced, so the glass is an indispensable component for realizing the purpose of the invention; if containing an excess of Bi2O3The stability of the glass is easily deteriorated, and if it is too small, it is difficult to satisfy the object of the present invention. Thus, Bi2O3The content of (B) is preferably 2 to 8%.
TiO2Is used for increasing the refractive index of glass, imparting high dispersion and reducing liquid phaseAny component effective at temperature, but if it is excessive, the devitrification of the glass tends to increase. Therefore, it is preferably 8% or less.
ZrO2Has the functions of improving the optical constant of the optical glass, improving the devitrification resistance and the chemical stability, and also has the functions of improving the refractive index and the dispersion. When the content of the additive is less than 3% by weight, the effect is not obvious, and when the content of the additive is more than 12% by weight, the melting property of the glass is reduced, and the crystallization property of the glass is deteriorated. Therefore, ZrO2The weight percentage of the components is controlled to be between 3 and 12 percent.
CaO has the functions of adjusting the refractive index and Abbe number of the glass, improving the chemical stability and the thermal stability of the glass, reducing the density of the glass, fluxing and improving the relative grinding hardness value of the glass. When the content is more than 10%, devitrification tendency of the glass increases, and when it is less than 1%, the effect of fluxing is not obtained. Therefore, the weight percentage content is controlled between 1 and 10 percent.
Sb2O3It can be optionally added as a defoaming agent, but it is sufficient that the content thereof is within 1% by weight, and if the content of Sb2O3 exceeds 0.2%, the coloring degree of the glass increases and the permeability becomes poor. Thus Sb2O3The content of the components is controlled to be 0-0.2%.
Examples
The optical glass of the present invention can be produced in the following manner: the raw materials are uniformly mixed to ensure that the contents of the components are within the specified range, the mixture is put into a platinum crucible, melted for 2-5h within the temperature range of 1250-1500 ℃ according to the melting difficulty of the glass composition, stirred and homogenized, then reduced to the proper temperature, finally cast into a mold and slowly cooled to obtain the glass.
The optical glasses shown in tables 1 to 2 (examples 1 to 18) were optical glasses obtained by weighing in accordance with the ratios of the respective examples shown in tables 1 to 2.
The results of composition, refractive index (nd), Abbe number (vd), and glass transition temperature (Tg) of example 1 of the present invention are shown in Table 1-2, where refractive index nd, Abbe number ν d: the test is carried out according to the test method of GB/T7962.1-2010 standard; glass transition temperature (Tg) was measured at room temperature using a TMA tester from PE corporation, usa; the density (. rho.) was measured according to the method specified in GB/T7962.20-2010. In these tables, the compositions of the respective components are expressed in% by weight.
TABLE 1
Figure GDA0002275639820000061
Figure GDA0002275639820000071
TABLE 2
Figure GDA0002275639820000072
Figure GDA0002275639820000081
The invention is optical glass with low cost, excellent chemical stability, high refraction and low dispersion, the refractive index is 1.815-1.851, the Abbe number is 42.6-49.8, and an optical element formed by the glass can meet the requirements of modern novel photoelectric products.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (8)

1. An optical glass with a high refractive index, characterized in that its composition, expressed in weight percentages, comprises: SiO 22：5-15％、B2O3：10-30％、La2O3：18-30％、Nb2O5：5-15％、Gd2O3：4-20％、Bi2O3：2-8％、TiO2：1-8％、ZrO2：3-12％、Ta2O5：2-10％、CaO：1-10％、Sb2O3: 0 to 0.2 percent; wherein said Bi2O3For doping with Zn2+Of Bi2O3(ii) a The Bi2O3Middle Zn2+The doping content of (A) is 5-10 wt%.
2. The high refractive index optical glass according to claim 1, further comprising Y2O3：1-10％。
3. A high refractive index optical glass according to claim 1 or 2, wherein 0.3. ltoreq. SiO in terms of weight percentage2/B2O3≤1.2。
4. An optical glass of high refractive index as defined in claim 1 or 2, wherein 1.5. ltoreq. La in weight percentage2O3/SiO2≤4。
5. An optical glass of high refractive index as defined in claim 1 or 2, wherein 0.4. ltoreq. La in% by weight2O3/(La2O3+Nb2O5+Gd2O3)≤0.6。
6. The high refractive index optical glass according to claim 1 or 2, wherein Bi is 8% by weight or more and less2O3+TiO2+ZrO2≤20％。
7. The high refractive index optical glass according to claim 1, wherein the Bi is prepared2O3The method comprises the following steps: dissolving bismuth nitrate in ethylene glycol, adding zinc salt, mixing, microwave heating in microwave reactor at power of 300-600W for 5-8 times for 2-6min, cooling, and passing throughAfter filtration, washing with water and absolute ethyl alcohol respectively, drying and roasting at the temperature of 500-600 ℃ for 1-2h to obtain the doped Zn2+Of Bi2O3。
8. High refractive index optical glass according to claim 1 or 2, wherein the density of the optical glass is less than 3.50g/cm3The glass transition temperature is 600 ℃ or lower.
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CN115244015A (en) * 2020-03-12 2022-10-25 豪雅株式会社 Optical glass and optical element
CN113511810B (en) * 2021-09-09 2021-11-26 南通市国光光学玻璃有限公司 High-refractive-index optical glass and preparation method thereof

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CN101367611B (en) * 2008-09-25 2011-09-28 成都光明光电股份有限公司 High-refractive index environment friendly weight lanthanum flint optical glass
CN102557117A (en) * 2012-03-08 2012-07-11 桂林理工大学 Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves
CN103319086A (en) * 2013-05-27 2013-09-25 都江堰市嘉杰光学有限责任公司 Optical glass with high refractive index and low dispersion, and preparation method thereof
CN103755137A (en) * 2014-01-24 2014-04-30 四川瑞天光学有限责任公司 High-refractive-index and low-dispersion optical glass and preparation method thereof
CN103969424B (en) * 2014-05-20 2015-07-22 武汉钢铁(集团)公司 Testing device and testing method for zinc corrosion resistance of refractory lining bricks
CN106848289B (en) * 2017-02-26 2020-04-14 桂林理工大学 Lotus root-like flaky spinel type ZnMn2O4Method for preparing powder

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