CN108409132B - Environment-friendly optical glass and optical element - Google Patents
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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
- C03C3/04—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
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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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
- C03C3/04—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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- 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
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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
本发明所要解决的技术问题是提供一种高折射率的环保光学玻璃和光学元件，该光学玻璃的折射率为1.69‑1.75、阿贝数为35‑43。环保光学玻璃，其重量百分比组成含有：Na2O：0.5‑5％；TiO2/(Na2O+K2O)：3.89‑10；TiO2/SiO2：0.23‑0.8；TiO2/B2O3：2.28‑8；SiO2+B2O3：25‑43％；Al2O3>SrO。本发明的环保光学玻璃不含有PbO、As2O3、氟化物等对环境有害的组分，化学稳定性好，析晶温度低，价格低廉，熔化性能良好。本发明玻璃适用于投影仪镜头、数码照相机、数码摄像机以及可拍照手机等设备。The technical problem to be solved by the present invention is to provide a high-refractive-index environment-friendly optical glass and an optical element. The optical glass has a refractive index of 1.69-1.75 and an Abbe number of 35-43. Environmentally friendly optical glass, its weight percentage composition contains: Na 2 O: 0.5-5%; TiO 2 /(Na 2 O+K 2 O): 3.89-10; TiO 2 /SiO 2 : 0.23-0.8; TiO 2 /B 2 O 3 : 2.28-8; SiO 2 +B 2 O 3 : 25-43%; Al 2 O 3 >SrO. The environmental protection optical glass of the invention does not contain PbO, As 2 O 3 , fluoride and other components harmful to the environment, and has good chemical stability, low crystallization temperature, low price and good melting performance. The glass of the invention is suitable for equipment such as projector lenses, digital cameras, digital video cameras, and camera phones.
Description
Technical Field
The present invention relates to an environment-friendly optical glass and an optical element, and particularly to an optical glass and an optical element having a refractive index (nd) of 1.69 to 1.75 and an abbe number (vd) of 35 to 43.
Background
In the face of the market pattern of extremely shrinking and extremely intense competition in the optical glass market, the research of PbO-free and As-free glass is strongly required2O3And fluoride, etc., and the glass is required to be low in price and excellent in quality, such as the characteristics of good chemical stability, good degree of coloration, low crystallization temperature and the like.
CN1105691C discloses an optical glass containing Nb2O5、Li2O and fluoride, which not only makes the glass expensive, but also raises the devitrification temperature and destroys the chemical stability of the glass. CN1044223C discloses an optical glass containing Nb2O5A large amount of TiO2、ZrO2、Li2O, etc., which also makes the glass expensive. CN1207230C discloses an optical glass containing a large amount of TiO in the glass component2The glass is colored to a high degree. CN101215084B discloses an optical glass containing a large amount of TiO in the glass component2And also contains fluoride, TiO2The coloring degree of the glass is deteriorated, the fluoride is easy to volatilize, the production difficulty is greatly increased, the chemical stability of the glass is damaged, and meanwhile, the environmental pollution is caused.
Disclosure of Invention
The invention aims to solve the technical problem of providing environment-friendly optical glass with high refractive index and an optical element, wherein the refractive index of the optical glass is 1.69-1.75, and the Abbe number is 35-43.
The technical scheme adopted by the invention for solving the technical problem is as follows: the environment-friendly optical glass comprises the following components in percentage by weight: na (Na)2O：0.5-5％；TiO2/(Na2O+K2O)：3.89-10；TiO2/SiO2：0.23-0.8；TiO2/B2O3：2.28-8；SiO2+B2O3：25-43％；Al2O3>SrO; the refractive index is 1.69-1.75, and Abbe number is 35-43.
Further, the weight percentage composition of the material comprises: SiO 22：20-39％；B2O3：0.5-6.9％；TiO2：3-15％；BaO：26-43％；ZnO：3-20％；Al2O3：0.5-8％；CaO：0-10％；La2O3：0-10％；ZrO2：0-10％；SrO：0-5％；K2O：0-5％；Sb2O3：0-0.5％。
The environment-friendly optical glass comprises the following components in percentage by weight: SiO 22：20-39％；B2O3：0.5-6.9％；TiO2：3-15％；BaO：26-43％；ZnO：3-20％；Na2O：0.5-5％；Al2O3：0.5-8％；CaO：0-10％；La2O3：0-10％；ZrO2：0-10％；SrO：0-5％；K2O：0-5％；Sb2O3: 0 to 0.5 percent; wherein Al is2O3>SrO。
Further, does not contain Li2O、Nb2O5、WO3、PbO、As2O3And fluorides.
The environment-friendly optical glass comprises the following components in percentage by weight: SiO 22：20-39％；B2O3：0.5-6.9％；TiO2：3-15％；BaO：26-43％；ZnO：3-20％；Na2O：0.5-5％；Al2O3：0.5-8％；CaO：0-10％；La2O3：0-10％；ZrO2：0-10％；SrO：0-5％；K2O：0-5％；Sb2O3：0-0.5％。
Further, the method can be used for preparing a novel materialWherein: SiO 22: 22 to 38 percent; and/or B2O3: 0.8-6%; and/or TiO2: 4.5-14.5%; and/or BaO: 28-41%; and/or ZnO: 3.5 to 18 percent; and/or Na2O: 0.5-4.5%; and/or Al2O3: 1 to 6 percent; and/or CaO: 0 to 9 percent; and/or La2O3: 0 to 8 percent; and/or ZrO2: 0 to 8 percent; and/or SrO: 0 to 2 percent; and/or K2O: 0 to 3.5 percent; and/or Sb2O3：0-0.3％。
Further, the content of the components meets one or more than one of the following 4 conditions:
1)SiO2+B2O3：25-43％；
2)TiO2/(Na2O+K2O)：3.89-10；
3)TiO2/SiO2：0.23-0.8；
4)TiO2/B2O3：2.08-8。
further, the content of the components meets one or more than one of the following 4 conditions:
1)SiO2+B2O3：28-40％；
2)TiO2/(Na2O+K2O)：3.89-8；
3)TiO2/SiO2：0.23-0.6；
4)TiO2/B2O3：2.18-7。
further, the water stability by the glass powder method is 1 type, and the acid stability by the powder method is 2 or more types.
Furthermore, the refractive index nd of the optical glass is 1.69-1.75, and the Abbe number vd is 35-43.
An optical element formed by the environment-friendly optical glass.
The invention has the beneficial effects that: the environment-friendly optical glass does not contain PbO and As2O3And fluoride and other components harmful to the environment, and has high chemical stability, low crystallization temperature, low cost and high smelting performance.The glass is suitable for equipment such as a projector lens, a digital camera, a digital video camera, a camera mobile phone and the like.
Detailed Description
The composition of the optical glass of the present invention will be described in detail below, and the content and the total content of each glass component are expressed in% by weight unless otherwise specified, and the ratio of the content to the total content of the glass component is expressed in terms of a weight ratio.
SiO2Is a product of the glass of the present invention, SiO2The optical glass has better chemical stability, reduces crystallization temperature, improves the degree of coloration of the glass and increases the high-temperature viscosity of the glass. If SiO2The content of (A) is less than 20%, a stable glass cannot be formed, and the chemical stability is poor; but if SiO2Above 39%, the refractive index of the glass cannot be within the required range. Thus, SiO2The content of (B) is 20-39%, preferably 22-38%.
B2O3The barium flint glass is also an optical glass network generation body oxide, can increase the stability of the glass, has good fluxing effect, and can well solve the problem of cylinder expansion of the barium flint glass. If B is present2O3The content of (A) is less than 0.5%, stable glass cannot be formed, the melting performance of the glass is poor, and the glass is easy to be heated; but if B is2O3Above 6.9%, the chemical stability of the glass may be deteriorated. Thus, B2O3The content of (B) is 0.5-6.9%, preferably 0.8-6%.
The inventor researches and discovers that SiO2And B2O3Total amount of (3) SiO2+B2O3When the content is limited to 25-43%, the glass forming performance and the melting performance of the glass are good, the high-temperature viscosity of the glass is proper, the phenomenon of foaming is avoided, and SiO2+B2O3The content of (B) is preferably 28 to 40%.
TiO2Is an intermediate oxide, is an effective component for realizing high refractive index and high dispersion of the glass, can improve the chemical stability of the glass and increase the stability of the glass. If TiO is present2Less than 3% of glassThe refractive index and Abbe number of glass cannot be in the required range; if, however, TiO2The content of (B) is more than 15%, the coloring degree of the glass is poor, and the design requirement cannot be met. Thus, TiO2The content of (B) is 3-15%, preferably 4.5-14.5%.
The inventor researches and discovers that when TiO is used2With SiO2Content ratio of TiO2/SiO2At 0.23-0.8, the glass has better chemical stability and good light transmittance, TiO2/SiO2The value of (A) is preferably 0.23 to 0.6. At the same time, when TiO2And B2O3Content ratio of TiO2/B2O3At 2.08-8, the glass has good glass forming performance and good permeability, and TiO2/B2O3The value of (A) is preferably 2.18 to 7.
BaO is an external body of the optical glass network, can effectively improve the refractive index of the optical glass and effectively expand the glass forming range of the glass. If the content of BaO is less than 26%, the refractive index and Abbe number of the glass cannot be within the desired ranges, and the melting property of the glass is poor; however, if the content of BaO is more than 43%, the glass has poor chemical stability and poor devitrification property. Therefore, the content of BaO is 26 to 43%, preferably 28 to 41%.
ZnO can effectively improve the optical constant of the glass, reduce the high-temperature viscosity of the optical glass, improve the chemical stability of the glass and obviously improve the devitrification resistance of the glass. If the content of ZnO is less than 3 percent, the chemical stability of the glass is poor, and the optical constant can not meet the requirement; however, if the content of ZnO is more than 20%, the chemical stability of the glass is rather poor and the glass forming property of the glass is also poor. Accordingly, the content of ZnO is 3 to 20%, preferably 3.5 to 18%.
Na2O is an essential component of the present invention, is an alkali metal oxide, is a preferable glass flux, can provide an optical glass having a good uniformity, and can improve the degree of coloration of the glass. If Na is contained in the glass2The content of O is lower than 0.5 percent, the viscosity of the glass is very high, and bubbles and poor internal problems are easy to occur; but if Na2The content of O is higher than 5%, the chemical stability of the glass is very highPoor crystallization property. Thus, Na2The content of O is 0.5 to 5%, preferably 0.5 to 4.5%.
K2O is also an alkali metal oxide and has better fluxing action. If K is2The content of O is more than 5%, the chemical stability of the glass is deteriorated, and the devitrification resistance is also lowered. Thus, K2The content of O is 0 to 5%, preferably 0 to 3.5%.
In particular, since the glass of the present invention does not contain Li2O, has the following advantages: 1) the glass has better chemical stability; 2) the glass has proper high-temperature viscosity and moderate material property, and is very beneficial to the forming of the glass; 3) the devitrification resistance of the glass is better.
The inventor researches and discovers that when TiO is used2/(Na2O+K2O) is 3.89-10, the glass has better transmittance, the network structure of the glass is more stable, the chemical stability is good, and TiO2/(Na2O+K2O) preferably has a value of 3.89 to 8.
Al2O3The density of the glass network structure can be improved, and the chemical stability of the glass can be effectively improved. If Al is present2O3The content of (A) is less than 0.5%, and the effect of improving the chemical stability cannot be achieved; but if Al is present2O3The content of (b) is more than 8%, the high-temperature viscosity of the glass becomes large, the melting property is poor, and there is a risk of devitrification. Thus, Al2O3The content of (B) is 0.5-8%, preferably 1-6%.
CaO can improve the glass glossiness and also can play a role in fluxing. If the content of CaO is more than 10%, the chemical stability of the glass may be poor and the risk of glass seizure may be large. Therefore, the CaO content is 0 to 10%, preferably 0 to 9%.
SrO belongs to one of alkaline earth metals, and can play a certain melting role when being added in a small amount. However, SrO has the following disadvantages in high-refractive index barite glasses, as compared with BaO and CaO: 1) in the high-refractive-index barite flint glass, the contribution to improving the refractive index and the dispersion of the glass is small, and even the effect of reducing is achieved; 2) for the barite with high refractive index, in order to improve the refractive index of the glass, more BaO is contained, the gas content in the molten glass is higher, if an oxide with melting property inferior to that of BaO is added, the glass is easy to generate foaming, and the glass with stable components can not be obtained; 3) SrO is more expensive than BaO and CaO, which causes the price of the glass to rise, and is extremely disadvantageous for manufacturing low-cost glass. Therefore, if the content of SrO is more than 5%, the chemical stability of the glass is deteriorated and the glass is very prone to develop. The SrO content is 0-5%, preferably 0-2%.
The inventors have found that Al is contained in the glass composition of the present invention2O3When the content is larger than the SrO content, i.e. Al2O3>SrO glass not only has good chemical stability, but also can reduce the gas content in the glass, eliminate the risk of glass foaming, obviously reduce the cost of the glass and obtain the glass with high refractive index.
ZrO2Can improve refractive index and dispersion of optical glass, and proper amount of ZrO2And the anti-devitrification capability and the chemical stability of the glass can be improved. If ZrO of2High content of (A), increased difficulty in melting glass, and easy occurrence of ZrO2Calculus, which can greatly increase the cost of glass. Thus, ZrO2The content of (B) is 0 to 10%, preferably 0 to 8%.
La2O3Is a common rare earth oxide, and can effectively improve the optical constant of the glass. If La is present2O3The content of (b) is more than 10%, the glass is easy to crystallize, and the glass cost is increased. Thus, La2O3The content of (B) is limited to 0 to 10%, preferably 0 to 8%.
Sb2O3Is a commonly used clarifying agent, and a proper amount of Sb2O3Is very beneficial to eliminating glass bubbles. However, the higher content of the component affects the transmittance of the glass. Thus, Sb2O3The content of (B) is 0 to 0.5%, preferably 0 to 0.3%.
The optical glass provided by the invention is prepared according to a preparation method well known to a person skilled in the art, namely: the raw materials are melted, clarified, stirred, homogenized, cooled to a proper temperature and formed, and the high-refractive-index environment-friendly optical glass with the refractive index (nd) of 1.69-1.75 and the Abbe number (vd) of 35-43 provided by the invention can be obtained.
The test method of each performance parameter of the optical glass provided by the invention comprises the following steps:
the refractive index and Abbe number are tested according to the GB/T7962.11-2010 colorless optical glass test method refractive index and dispersion coefficient.
Water-resistant stability by glass powder method DWMeasured using the GB/T17129 test standard.
Acid stability by glass powder method DAMeasured using the GB/T17129 test standard.
Through the tests, the obtained optical glass of the invention has the following properties: refractive index (nd) of 1.69-1.75, Abbe number (vd) of 35-43, and water-resistant stability (D)W) Is of type 1, acid-resistant stability (D)A) Is more than 2 types. No PbO, no As2O3Free of fluoride and free of Li2O、Nb2O5、WO3And the like, good melting property, low price and high refractive index.
The present invention also provides an optical element formed of the above-mentioned optical glass of the present invention, and therefore the optical element has all the characteristics of the above-mentioned optical glass of the present invention. The optical element provided by the invention is suitable for being applied to equipment such as a projector lens, a digital camera, a digital video camera and the like.
Examples
In order to further understand the technical solution of the present invention, preferred embodiments of the present invention will be described with reference to the following specific examples. It is to be noted and understood that these examples are only for the purpose of better illustrating the features and advantages of the present invention, and do not limit the claims of the present invention.
The optical glass provided in examples 1 to 30 of the present invention has the components in the weight percentages and the corresponding properties shown in tables 1 to 3. The required optical glass can be obtained by weighing the components of the optical glass in the embodiments of tables 1-3 according to the ratio, fully mixing the components uniformly, adding the components into an optical glass melting furnace, melting, clarifying, stirring and homogenizing the components at a proper process temperature, cooling the components to a proper temperature, pouring the molten glass into a preheated metal mold for molding and annealing. The composition and the corresponding properties of the optical glass of the invention are as follows: the results of refractive index (nd), dispersion (nF-nC), Abbe number (vd) and chemical stability are shown in examples 1 to 30 in tables 1 to 3.
TABLE 1
TABLE 2
TABLE 3
As can be seen from the above examples, the environment-friendly optical glass provided by the invention is free of PbO and As2O3Free of fluoride and free of Li2O、Nb2O5、WO3And the like, and has excellent environmental protection performance and good melting performance, the refractive index (nd) is 1.69-1.75, and the Abbe number (vd) is 35-43. The optical glass is suitable for equipment such as a projector lens, a digital camera, a digital video camera and the like.
Claims (12)
1. The environment-friendly optical glass is characterized by comprising the following components in percentage by weight: na (Na)2O：0.5-5%；B2O3：0.5-5.49%；TiO2：6-15%；TiO2/（Na2O+K2O）：3.89-10；TiO2/SiO2：0.30-0.8；TiO2/B2O3：2.28-8；SiO2+B2O3：25-43%；Al2O3>SrO; the refractive index is 1.69-1.75, and Abbe number is 35-41.12.
2. The environment-friendly optical glass according to claim 1, which comprises the following components in percentage by weight: SiO 22：20-39%；BaO：26-43%；ZnO：3-20%；Al2O3：0.5-8%；CaO：0-10%；La2O3：0-10%；ZrO2：0-10%；SrO：0-5%；K2O：0-5%；Sb2O3：0-0.5%。
3. The environment-friendly optical glass is characterized by comprising the following components in percentage by weight: SiO 22：20-39%；B2O3：0.5-5.49%；TiO2：6-15%；BaO：26-43%；ZnO：3-20%；Na2O：0.5-5%；Al2O3：0.5-8%；CaO：0-10%；La2O3：0-10%；ZrO2：0-10%；SrO：0-5%；K2O：0-5%；Sb2O3: 0 to 0.5 percent; wherein Al is2O3>SrO，TiO2/SiO2: 0.30-0.8, Abbe number 35-41.12.
4. The eco-friendly optical glass according to any one of claims 1 to 3, not containing Li2O、Nb2O5、WO3、PbO、As2O3And fluorides.
5. The environment-friendly optical glass is characterized by comprising the following components in percentage by weight: SiO 22：20-39%；B2O3：0.5-6.9%；TiO2：6-15%；BaO：26-43%；ZnO：3-20%；Na2O：0.5-5%；Al2O3：0.5-8%；CaO：0-10%；La2O3：0-10%；ZrO2：0-10%；SrO：0-5%；K2O：0-5%；Sb2O3：0-0.5%，TiO2/SiO2: 0.30-0.8, Abbe number 35-41.12.
6. The eco-friendly optical glass of claim 5, wherein: SiO 22: 22 to 38 percent; and/or B2O3: 0.8-6%; and/or TiO2: 6 to 14.5 percent; and/or BaO: 28-41%; and/or ZnO: 3.5 to 18 percent; and/or Na2O: 0.5-4.5%; and/or Al2O3: 1 to 6 percent; and/or CaO: 0 to 9 percent; and/or La2O3: 0 to 8 percent; and/or ZrO2: 0 to 8 percent; and/or SrO: 0 to 2 percent; and/or K2O: 0 to 3.5 percent; and/or Sb2O3：0-0.3%。
7. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: SiO 22: 22 to 38 percent; and/or B2O3: 0.8 to 5.49 percent; and/or TiO2: 6 to 14.5 percent; and/or BaO: 28-41%; and/or ZnO: 3.5 to 18 percent; and/or Na2O: 0.5-4.5%; and/or Al2O3: 1 to 6 percent; and/or CaO: 0 to 9 percent; and/or La2O3: 0 to 8 percent; and/or ZrO2: 0 to 8 percent; and/or SrO: 0 to 2 percent; and/or K2O: 0 to 3.5 percent; and/or Sb2O3：0-0.3%。
8. An optical glass according to claim 3 or 5, characterized in that the content of the composition satisfies one or more of the following 3 conditions:
1）SiO2+B2O3：25-43%；
2）TiO2/（Na2O+K2O）：3.89-10；
3) TiO2/B2O3：2.08-8。
9. the optical glass according to any one of claims 1 to 3 and 5, wherein the content of the composition satisfies one or more of the following 4 conditions:
1）SiO2+B2O3：28-40%；
2）TiO2/（Na2O+K2O）：3.89-8；
3) TiO2/SiO2：0.30 -0.6；
4) TiO2/B2O3：2.18-7。
10. the optical glass according to any one of claims 1 to 3 and 5, wherein the glass powder method has a water resistance stability DWClass 1, acid stability by powder method DAIs more than 2 types.
11. An optical glass according to claim 3 or 5, wherein the refractive index nd of the optical glass is from 1.69 to 1.75.
12. An optical element formed by using the eco-friendly optical glass as defined in any one of claims 1 to 11.
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| CN111217519A (en) * | 2018-11-27 | 2020-06-02 | 宜城市泳瑞玻璃科技有限公司 | Environment-friendly optical glass |
| CN109626813B (en) * | 2019-01-07 | 2021-08-31 | 成都光明光电股份有限公司 | Optical glass, optical preforms, optical components and optical instruments |
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| CN108409132A (en) | 2018-08-17 |
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