CN111018342A - Optical glass, glass preform, optical element and optical instrument - Google Patents
Optical glass, glass preform, optical element and optical instrument Download PDFInfo
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- CN111018342A CN111018342A CN201911346192.0A CN201911346192A CN111018342A CN 111018342 A CN111018342 A CN 111018342A CN 201911346192 A CN201911346192 A CN 201911346192A CN 111018342 A CN111018342 A CN 111018342A
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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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- 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 provides an optical glass, which comprises the following components in percentage by weight: SiO 22：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3: 10 to 45% of Al2O3/B2O30.5 to 4.0. Through reasonable component design, the optical glass has the advantages of 1.65-1.78 refractive index and 49-56 Abbe number, has excellent chemical stability and lower thermal expansion coefficient, and is suitable for being used in the fields of vehicle-mounted monitoring and security protection and the like.
Description
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.65-1.78 and an Abbe number of 49-56, and a glass prefabricated member, an optical element and an optical instrument which are made of the optical glass.
Background
The lanthanum-containing optical glass with the refractive index of 1.65-1.78 and the Abbe number of 49-56 belongs to lanthanum crown glass, has the advantages of high refractive index and low dispersion compared with common crown glass, and can greatly improve the field angle of a lens and improve the imaging quality when being applied to an optical imaging system.
With the development of intelligent driving technology, intelligent security technology and environment perception technology, the lens in the field needs to work in severe environments such as sand storm, acid rain, high-low temperature alternation and the like for a long time and keeps extremely high reliability, which puts forward a new requirement on the environmental stability of the lens material, different from the traditional lens (such as a single lens reflex) working in a better environment. Taking a vehicle-mounted lens as an example, the requirement of large field of view and high definition requires that the material has the characteristics of high refractive index and low dispersion. More importantly, the vehicle-mounted lens is safe to life, the design service life of the vehicle-mounted lens is consistent with the service life of a vehicle, more than 15 years are needed, and extremely high requirements are provided for the reliability of the vehicle-mounted lens.
The vehicle-mounted lens needs to consider better acid resistance, such as resistance to acid rain, acid snow-melting agents and the like. At present, lanthanum crown glass is mainly composed of B2O3-La2O3The system composition, the acid resistance of the powder method can only reach 3 types or lower, and the powder method is easy to be corroded by acid substances when used under long-term severe conditions and is difficult to meet the use requirements of the vehicle-mounted field.
The vehicle-mounted lens also needs to be considered to be capable of bearing thermal shock and achieving stable operation in extremely high and low temperature environments. If the temperature of the automobile is very high after the automobile runs for a long time in a hot environment, if the automobile suddenly meets rainfall, water pits, car washing and the like, the lens material is subjected to great temperature impact, and if the temperature impact resistance is poor, the lens has the risk of breakage. This translates into a requirement for the glass properties, i.e., a requirement for the glass to have a low coefficient of thermal expansion.
Disclosure of Invention
Based on the above factors, the technical problem to be solved by the present invention is to provide a high-refractive index low-dispersion optical glass having excellent chemical stability and a low thermal expansion coefficient.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) the optical glass comprises the following components in percentage by weight: SiO 22：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3: 10 to 45% of Al2O3/B2O30.5 to 4.0.
(2) The method according to (1)The optical glass comprises the following components in percentage by weight: ZrO (ZrO)2: 0-8%, and/or MgO: 0 to 8%, and/or P2O5: 0 to 5%, and/or Gd2O3: 0 to 10%, and/or TiO2: 0 to 10%, and/or Nb2O5: 0-5%, and/or ZnO: 0-10%, and/or CaO: 0-8%, and/or SrO + BaO: 0 to 8%, and/or Li2O: 0 to 4%, and/or Na2O: 0 to 4%, and/or K2O: 0-4%, and/or a clarifying agent: 0 to 2 percent.
(3) Optical glass, the composition of which is expressed in weight percentage by SiO2：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3：10～45％、ZrO2：0～8％、MgO：0～8％、P2O5：0～5％、Gd2O3：0～10％、TiO2：0～10％、Nb2O5：0～5％、ZnO：0～10％、CaO：0～8％、SrO+BaO：0～8％、Li2O：0～4％、Na2O：0～4％、K2O: 0-4% of a clarifying agent: 0 to 2% of Al2O3/B2O30.5 to 4.0.
(4) Optical glass containing SiO2、B2O3、Al2O3、R2O3And RO, wherein Al2O3/B2O30.5 to 4.0, the refractive index n of the optical glassd1.65-1.78, Abbe number vd49 to 56, coefficient of thermal expansion α100/300℃Is 75X 10-7below/K, said R2O3Is La2O3、Y2O3、Gd2O3R0 is one or more of MgO, CaO, SrO and BaO.
(5) The optical glass according to (4), which comprises the following components in percentage by weight: SiO 22：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3：10～45％、ZrO2：0～8％、MgO：0～8％、P2O5：0～5％、Gd2O3：0～10％、TiO2：0～10％、Nb2O5：0～5％、ZnO：0～10％、CaO：0～8％、SrO+BaO：0～8％、Li2O：0～4％、Na2O：0～4％、K2O: 0-4% of a clarifying agent: 0 to 2 percent.
(6) The optical glass according to any one of (1) to (5), which has a composition satisfying, in terms of weight percent, one or more of the following 5 conditions:
1)Al2O3/B2O30.7 to 3.5;
2)Al2O3/SiO20.4 to 2.0;
3)La2O3/Y2O30.5 to 2.1;
4) CaO/MgO is 0-1.2;
5)(Na2O+K2O)/Li2o is 0 to 1.1.
(7) The optical glass according to any one of (1) to (5), which comprises, in terms of weight percent: SiO 22: 12-28%, and/or B2O3: 7 to 18%, and/or Al2O3: 12-30% and/or La2O3: 18 to 35%, and/or Y2O3: 13 to 40%, and/or ZrO2: 0.5-6%, and/or MgO: 0.5 to 6%, and/or P2O5: 0 to 3%, and/or Gd2O3: 0 to 5%, and/or TiO2: 0 to 5%, and/or Nb2O5: 0-3%, and/or ZnO: 0.5-8%, and/or CaO: 0-6%, and/or SrO + BaO: 0 to 4%, and/or Li2O: 0 to 3%, and/or Na2O: 0 to 3%, and/or K2O: 0-3%, and/or a clarifying agent: 0 to 1 percent.
(8) The optical glass according to any one of (1) to (5), which has a composition satisfying, in terms of weight percent, one or more of the following 5 conditions:
1)Al2O3/B2O30.8 to 3.0;
2)Al2O3/SiO20.5 to 1.8;
3)La2O3/Y2O30.6 to 1.9;
4) CaO/MgO is 0-1.0;
5)(Na2O+K2O)/Li2o is 0 to 1.0.
(9) The optical glass according to any one of (1) to (5), which comprises, in terms of weight percent: SiO 22: 14 to 25%, and/or B2O3: 9 to 16% and/or Al2O3: 14 to 22%, and/or La2O3: 20 to 30%, and/or Y2O3: 15 to 35%, and/or ZrO2: 0.5-4%, and/or MgO: 0.5-4%, and/or ZnO: 0.5-5%, and/or CaO: 0 to 3%, and/or Li2O: 0.1-2%, and/or a clarifying agent: 0 to 0.5 percent.
(10) The optical glass according to any one of (1) to (5), which has a composition satisfying, in terms of weight percent, one or more of the following 4 conditions:
1)Al2O3/SiO20.7 to 1.4;
2)La2O3/Y2O30.7 to 1.7;
3) CaO/MgO is 0-0.8;
4)(Na2O+K2O)/Li2o is 0 to 0.8.
(11) The optical glass according to any one of (1) to (5), wherein P is not contained in the component2O5And/or does not contain Gd2O3And/or does not contain TiO2And/or no Nb2O5And/or does not contain BaO, and/or does not contain SrO, and/or does not contain K2O, and/or does not contain Na2O。
(12) The optical glass according to any one of (1) to (5), which isRefractive index n ofd1.65 to 1.78, preferably 1.68 to 1.74; abbe number vd49 to 56, preferably 50 to 54.
(13) The optical glass according to any one of (1) to (5), which has stability against acid action DAIs more than 3 types, and preferably has acid resistance stability DAIs more than 2 types; and/or a temperature coefficient of refractive index dn/dt of 10.0 x 10-6A temperature coefficient of refractive index dn/dt of 9.0X 10 is preferably not more than/° C-6A temperature coefficient of refractive index dn/dt of 8.5X 10 or less-6A temperature coefficient of refractive index dn/dt of 8.0X 10 or less-6Below/° c; and/or lambda80Is less than or equal to 405nm, preferably lambda80Is less than or equal to 400nm, more preferably lambda80Is less than or equal to 395 nm; and/or Knoop hardness HKIs 680 x 107Pa or more, preferably Knoop hardness HKIs 685 × 107Pa or more, more preferably Knoop hardness HKIs 690X 107Pa or more, and/or a coefficient of thermal expansion α100/300℃Is 75X 10-7below/K, the thermal expansion coefficient is preferably α100/300℃Is 73X 10-7A thermal expansion coefficient of α or less is more preferable100/300℃Is 70X 10-7and/K is less than or equal to.
(14) A glass preform made of the optical glass according to any one of (1) to (13).
(15) An optical element produced from the optical glass according to any one of (1) to (13) or the glass preform according to (14).
(16) An optical device produced using the optical glass of any one of (1) to (13) or the optical element of (15).
The invention has the beneficial effects that: through reasonable component design, the optical glass has the advantages of 1.65-1.78 refractive index and 49-56 Abbe number, has excellent chemical stability and lower thermal expansion coefficient, and is suitable for being used in the fields of vehicle-mounted monitoring and security protection and the like.
Detailed Description
The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. The optical glass of the present invention may be simply referred to as glass in the following.
[ optical glass ]
The ranges of the respective components of the optical glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect 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 (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 herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.
The optical glass of the present invention mainly contains SiO2、B2O3、Al2O3Lanthanide metal oxides R2O3(R2O3Is La2O3、Y2O3、Gd2O3One or more of the above compounds) and alkaline earth metal oxide RO (R0 is one or more of MgO, CaO, SrO and BaO), by a reasonable component distribution ratio, an optical glass having a refractive index of 1.65 to 1.78 and an Abbe number of 49 to 56 is formed, and the optical glass has excellent chemical stability and a low thermal expansion coefficient, and by optimizing the mixture ratio, further, the optical glass can obtain performances such as a low temperature coefficient of refractive index and a high transmittance, and is suitable for use under severe conditions.
< essential Components and optional Components >
The skeleton of the optical glass is mainly made of SiO2、B2O3、P2O5And the like.
SiO2The formed glass skeleton is compact, can improve the stability of acid resistance of glass, and is combined with B2O3、P2O5In comparison with the other two network forming oxides, SiO2The refractive index of (2) is low and the dispersion is large. If SiO2In excess of 30%, the refractive index and dispersion of the glass may be lower than the design requirements, while also presenting a risk of being difficult to melt; if the content is less than 10%, the stability of the glass against acid action is drastically deteriorated. On the other hand, since the glass of the present invention contains a large amount of rare earth metal oxide and risks rapid deterioration of devitrification resistance of the glass, SiO is used for balancing the refractive index, dispersion, stability of acid resistance and resistance to devitrification of the optical glass of the present invention2The content of (b) is limited to 10 to 30%, preferably 12 to 28%, more preferably 14 to 25%.
B2O3The glass can be added into the glass of the invention to improve the refractive index of the glass and reduce the dispersion of the glass. However, if the content exceeds 20%, the following problems are caused to the glass of the present invention: 1) the acid resistance of the glass decreases sharply. The inventors have found through extensive studies that the glass system of the present invention contains a small amount of alkali metals and a large amount of Al2O3If B is2O3The content of (b) exceeds 20%, and the structure thereof rapidly changes abruptly in the direction of porosity, thereby causing a sharp decrease in acid resistance of the glass. 2) If the glass according to the invention is to be strengthened further by means of chemical strengthening (ion exchange), B2O3The increase of the content hinders ion exchange on the surface of the glass, thereby reducing the chemical strengthening effect, and if the content exceeds 20%, the glass is difficult to increase the strength by the chemical strengthening method. 3) B is2O3The higher the content of (A), the stronger the ability to corrode the refractory material, more impurity elements are brought in during the production process, and the transmittance of the product is reduced. Thus, in the present invention B2O3The upper limit of the content of (B) is 20%, preferably 18%, more preferablyThe upper limit is selected to be 16%.
On the other hand, B2O3When the content of (b) is less than 5%, the dispersion of the glass is higher than the design requirement, and the glass is particularly liable to devitrify, resulting in deterioration of the melting property of the glass raw material. Thus, B2O3The lower limit of (B) is 5%, the lower limit is preferably 7%, and the lower limit is more preferably 9%.
Proper amount of P2O5The glass dispersion can be reduced and the chemical strengthening performance of the glass can be improved when the glass is added into the glass, but if the content of the glass exceeds 5 percent, the glass has serious ceramization tendency, the volatilization amount is increased in the smelting process, and the controllability of key indexes such as refractive index, dispersion and the like is reduced. Thus, P2O5The content of (B) is limited to 5% or less, preferably 3% or less, and more preferably no P is added2O5。
Al2O3Is the main component of the glass of the invention, the content of which added to the glass is SiO2、B2O3And alkali metal oxides (e.g., Li)2O、Na2O、K2O, etc.) and the like. The inventors have found that Al changes when other components of the glass are changed2O3The effect therein also changes. Specifically, 1) when the content of the alkali metal oxide is less than 2%, Al2O3The maximum addition amount of the glass can reach 35 percent, the acid resistance of the glass is greatly improved, meanwhile, the thermal expansion coefficient of the glass is rapidly reduced, and the thermal shock resistance is obviously improved; if the content is more than 35%, the melting property of the glass is rapidly deteriorated, and a large amount of infusible matter appears in the glass even if an extremely high melting temperature is used. 2) When the content of the alkali metal oxide is more than 2%, the chemical strengthening property of the glass is enhanced, but it is required to control Al2O3Below 30%, otherwise the glass raw material becomes extremely refractory. 3) If Al is present2O3The content of (b) is less than 10%, the acid resistance of the glass is rapidly reduced, and the thermal expansion coefficient of the glass is rapidly increased, so that the thermal shock resistance of the glass is greatly reduced. Thus, Al2O3The content of (B) is 10 to 35%, preferably 12 to 30%, more preferably 14 to 22% in the present invention.
In the present glass system, Al2O3Content of (D) and SiO2、B2O3The content of (A) is closely related to the content of (B) because of Al3 +Ions in the glass structure will follow SiO2、B2O3The content change of (a) produces a structural change, thereby affecting the refractive index, acid resistance and thermal shock resistance of the glass. When Al is present2O3/B2O3When the value of (b) is less than 0.5, the dispersion of the glass is higher than the design requirement, and the acid resistance of the glass is rapidly reduced; if Al is present2O3/B2O3When the value of (b) is more than 4.0, the thermal expansion coefficient of the glass stops decreasing and the glass material becomes extremely refractory. Thus, Al2O3/B2O3The value of (b) is 0.5 to 4.0, preferably 0.7 to 3.5, and more preferably 0.8 to 3.0.
When Al is present2O3/SiO2When the value of (b) is higher than 2.0, the hardness and acid resistance of the glass stop rising rapidly and tend to decrease, while the glass becomes extremely refractory and the transmittance remarkably decreases; al (Al)2O3/SiO2When the value of (A) is less than 0.4, the temperature coefficient of the glass refractive index rapidly rises, failing to meet the design requirements. Thus, Al2O3/SiO2The value of (b) is 0.4 to 2.0, preferably 0.5 to 1.8, and more preferably 0.7 to 1.4.
The traditional lanthanum crown optical glass generally adopts La2O3To achieve high refractive index and low dispersion, a large amount of La is introduced to achieve the desired refractive index2O3. The inventor researches and discovers that the La is too high2O3The problem that the acid resistance and the thermal shock resistance of the glass cannot meet the design requirements due to the deterioration of the acid resistance and the improvement of the thermal expansion coefficient of the glass is caused in Al2O3The content is more obvious when the content is more than 10 percent. However, if La is not added2O3The refractive index and dispersion of the glass do not meet the design requirements. Therefore, to ensure that the refractive index and Abbe number of the glass of the present invention meet the design expectations, La2O3The content of (A) is more than 15%Preferably 18% or more, and more preferably 20% or more. If La2O3The content of (b) is more than 40%, the acid resistance of the glass is rapidly deteriorated, and the thermal expansion coefficient is rapidly increased, so that the content is 40% or less, preferably 35% or less, and more preferably 30% or less.
In the invention, 45% or less of Y is introduced2O3Can reduce La2O3In the same time of using Y3+The ion field has the advantage of high intensity, so that the acid resistance of the glass is improved and the thermal expansion coefficient of the glass is reduced while high refractive index and low dispersion are realized; if Y is2O3The addition amount of the glass is less than 10 percent, the acid resistance and the thermal shock resistance of the glass can not meet the design requirements, and the hardness of the glass is reduced. Thus, Y in the present invention2O3The content of (b) is 10 to 45%, preferably 13 to 40%, more preferably 15 to 35%.
Further, the inventors have found that when La is used2O3/Y2O3When the value of (b) is more than 2.1, the acid resistance of the glass is rapidly decreased; when La2O3/Y2O3When the value of (A) is less than 0.5, the temperature coefficient of refractive index of the glass rapidly rises, and the glass does not meet the design requirement, and simultaneously the stability of the glass rapidly falls. Thus, La2O3/Y2O3When the value of (A) is in the range of 0.5 to 2.1, preferably 0.6 to 1.9, more preferably 0.7 to 1.7, the acid resistance, temperature coefficient of refractive index and glass stability of the glass are most balanced.
An appropriate amount of Gd2O3The addition to the glass can reduce the tendency of the glass to devitrify, especially in the Y2O3The effect is more remarkable when the content exceeds 20%, but if the content exceeds 10%, the devitrification resistance of the glass is sharply reduced. Thus, Gd2O3The content of (b) is limited to 10% or less, preferably 5% or less. In some embodiments, it is more preferable not to add Gd if the glass has a margin in devitrification resistance2O3。
Appropriate amount of TiO2The thermal expansion coefficient of the glass can be rapidly reduced by adding the glass into the glass, so that the glass is resistant toThe thermal shock capability is rapidly improved. However, TiO2The dispersion is large, and if the content exceeds 10%, the dispersion of the glass is higher than the design requirement. More importantly, since the glass of the present invention has less free oxygen, more than 10% TiO2The addition to the glass causes a sharp decrease in transmittance. Thus, TiO2The content of (b) is limited to 10% or less, preferably 5% or less. In some embodiments, it is more preferable not to add TiO if the glass has a margin in its thermal shock resistance2。
Appropriate amount of ZrO2The addition of the ZrO-based ceramic powder into glass can reduce the thermal expansion coefficient of the glass and improve the acid resistance of the glass, if ZrO is added into the glass2The content exceeding 8% deteriorates glass meltability, and brings about the risk of lowering transmittance and inclusion, so that ZrO in the present invention2The content is below 8%. In some embodiments, if ZrO2The content is less than 0.5 percent, and the corrosion of the glass to refractory materials in the melting process is increased rapidly, thereby bringing about the problems of transmittance reduction and smelting furnace service life reduction. Thus, ZrO2The content of (b) is preferably 0.5 to 8%, more preferably 0.5 to 6%, and further preferably 0.5 to 4%.
Nb2O5The addition of the glass into the glass can improve the refractive index of the glass and the stability of the glass, but the dispersion is large, and if the addition amount exceeds 5%, the dispersion of the glass cannot meet the design requirement, so the content of the glass is limited to be less than 5%. Nb with a margin of glass stability2O5The content is preferably 3% or less, and more preferably no Nb is added2O5。
The addition of an appropriate amount of ZnO to the glass can lower the thermal expansion coefficient of the glass, raise the refractive index of the glass, and particularly, it is important to raise the acid resistance of the glass, and if the content is more than 10%, the dispersion of the glass is higher than the design requirement, and the hardness of the glass is lower than the design requirement, so that the content of ZnO is limited to 10% or less. In some embodiments, when the content of ZnO is less than 0.5%, the effect of improving acid resistance is not significant, and the content of ZnO is preferably 0.5 to 8%, and more preferably 0.5 to 5%.
MgO, CaO, SrO and BaO belong to alkaline earth metal oxides, and when the MgO, the CaO, the SrO and the BaO are added into glass, the refractive index of the glass can be improved, and the stability of the glass can be improved. The inventors have found through studies that the introduction of alkaline earth metal oxides, particularly BaO and SrO, greatly reduces the acid resistance of the glass, and at the same time, the thermal expansion coefficient of the glass rapidly increases, and the thermal shock resistance of the glass decreases.
The inventor further researches and discovers that the stability of the glass can be improved by introducing proper amount of MgO and CaO, the acid resistance is not reduced basically, and the hardness and the thermal shock resistance of the glass are slightly improved. Therefore, in the present invention, the alkaline earth metal oxide is preferably introduced as MgO and CaO.
The MgO can improve the thermal shock resistance of the glass while adjusting the stability of the glass, but if the content of the MgO exceeds 8 percent, the devitrification resistance of the glass is rapidly reduced, and the glass is cerammed even in smelting, so the content of the MgO is limited to be below 8 percent. In some embodiments, if the MgO content is less than 0.5%, the stability of the glass is degraded and the thermal shock resistance of the glass is degraded. Therefore, the content of MgO is preferably 0.5 to 8%, more preferably 0.5 to 6%, and still more preferably 0.5 to 4%. The proper amount of CaO added into the glass can obviously improve the hardness of the glass, but if the content of CaO exceeds 8 percent, the acid resistance of the glass is rapidly reduced, and the thermal expansion coefficient of the glass is rapidly increased. Therefore, the content of CaO is limited to 0 to 8%, preferably 0 to 6%, and more preferably 0 to 3%.
In some embodiments of the present invention, the stability, acid resistance and hardness of the glass are most balanced when the CaO/MgO value is between 0 and 1.2, preferably between 0 and 1.0, and more preferably between 0 and 0.8.
In some embodiments, if the glass has a margin in acid and thermal shock resistance, the stability of the glass can be further improved by adding appropriate amounts of BaO and SrO, but the total content of BaO and SrO, BaO + SrO, should not exceed 8%. Therefore, the content of BaO + SrO is 0 to 8%, preferably 0 to 4%, and more preferably BaO and SrO are not added.
Li2O、Na2O、K2O is an alkali metal oxide, and it is believed that the addition of alkali metal oxides to glass rapidly degrades the glassThe acid resistance of the glass increases the thermal expansion coefficient of the glass, resulting in a decrease in the thermal shock resistance. The inventor finds that the melting temperature of the glass can be reduced and the transmittance of the glass can be improved by adding the proper type and the proper amount of alkali metal oxide into the glass; the glass has low content of alkali earth metal and contains more B2O3The addition of a small amount of alkali metal oxide may not reduce or slightly improve the acid resistance and thermal shock resistance, on the contrary. More importantly, the glass has the chemical strengthening capability by adding a proper amount of alkali metal oxide, and the thermal shock resistance of the glass can be greatly improved by the chemical strengthening.
The inventors have further investigated and found that a suitable amount of Li2O does not damage the acid resistance of the glass, can also reduce the thermal expansion coefficient of the glass, and more importantly, can greatly reduce the melting temperature of the glass; however, Li2When the O content exceeds 4%, the hardness of the glass is greatly deteriorated. Thus, Li2The content of O is limited to 4% or less, preferably 3% or less, and Li is more preferable in view of lowering the high-temperature viscosity of the glass2The content of O is 0.1-2%.
In some embodiments, in the case of glass having a margin in thermal shock resistance and hardness, 4% or less of Na may be added2O to lower the high temperature viscosity of the glass, preferably Na2The content of O is 3% or less, and Na is preferably not added2O。
In some embodiments, less than 4% K may be added with a margin in the thermal shock resistance and hardness of the glass2O to lower the high temperature viscosity of the glass, preferably Na2The content of O is 3% or less, and it is more preferable not to add K2O。
In some embodiments, when Li is present in the glass2When it is O, (Na)2O+K2O)/Li2When the value of O is 0 to 1.1, preferably 0 to 1.0, more preferably 0 to 0.8, the glass has an appropriate thermal expansion coefficient and acid resistance and is most excellent in chemical strengthening performance.
In some embodiments of the invention, 0-2% is addedSb (A) of2O3、SnO2SnO, NaCl, sulfate and CeO2As a clarifying agent, preferably Sb is used2O3As a fining agent, the fining effect of the glass can be improved. However, the invention has reasonable formula design, good clarification effect and excellent bubble degree, so 0-1% of clarifier is preferably added, 0-0.5% of clarifier is more preferably added, and no clarifier is further preferably introduced.
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, 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.
In order to achieve environmental friendliness, the optical glass of the present invention does not contain As2O3And PbO. Although As2O3Has the effects of eliminating bubbles and better preventing the glass from coloring, but As2O3The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As2O3All cause environmental pollution.
The "no incorporation", "no inclusion", "no addition" and "0%" described herein mean that the compound, molecule, element or the like is not intentionally added as a raw material to the optical glass of the present invention; however, it is 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 optical glass and may be contained in the final optical glass in small or trace amounts.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (n) of optical glassd) And Abbe number (v)d) The test was carried out according to the method specified in GB/T7962.1-2010.
Refractive index (n) of the optical glass of the present inventiond) 1.65 to 1.78, preferably 1.68 to 1.74; abbe number (v)d) 49 to 56, preferably 50 to 54.
< stability against acid Effect >
Stability of acid resistance of optical glass (D)A) (powder method) the test was carried out according to the method prescribed in GB/T17129. Acid resistance stability is sometimes referred to herein simply as acid resistance.
Stability of acid resistance of the optical glass of the present invention (D)A) Is 3 or more, preferably 2 or more.
< temperature coefficient of refractive index >
The temperature coefficient of refractive index (dn/dt) of optical glass was measured according to the method specified in GB/T7962.4-2010, and the temperature coefficient of refractive index (d-line dn/dt relative (10)) was measured in the range of 20 to 40 deg.C-6/℃))。
The temperature coefficient of refractive index (dn/dt) of the optical glass of the present invention is 10.0X 10-6Preferably 9.0X 10 or less/° C-6Lower than/° C, more preferably 8.5X 10-6Preferably not more than 8.0X 10/° C-6Below/° c.
< degree of coloration >
Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention80) And (4) showing. Lambda [ alpha ]80Refers to the wavelength, lambda, corresponding to a glass having a transmittance of 80%80Was measured using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished, measuring the spectral transmittance in the wavelength region from 280nm to 700nm and showing a wavelength of transmittance of 80%. 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. Thus, in high refractive index glasses, λ80A small value of (a) means that the glass itself is colored very little.
Optical glass lambda of the present invention80In the range of less than or equal to 405nm, preferably lambda80In the range of less than or equal to 400nm, more preferably λ80Is less than or equal to 395 nm.
< Knoop hardness >
Knoop hardness (H) of optical glassK) The test is carried out by using the method specified in GB/T7962.18-2010.
Knoop hardness (H) of the optical glass of the present inventionK) Is 680 x 107Pa or more, preferably 685X 107Pa or more, more preferably 690X 107Pa or above.
< coefficient of thermal expansion >
Thermal expansion coefficient (α) of optical glass at 100-300 DEG C100/300℃) Testing according to the method specified in GB/T7962.16-2010.
Thermal expansion coefficient (α) of the optical glass of the present invention100/300℃) Is 75X 10-7Preferably 73X 10 or less,/K-7A value of 70X 10 or less, more preferably-7and/K is less than or equal to.
[ production method ]
The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1300-1350 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Glass preform and optical element
The glass preform can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass preform may be produced by machining the optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the optical glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing.
It should be noted that the means for producing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
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 has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.
Examples of the lens include 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.
[ optical instruments ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, vehicle-mounted equipment, camera equipment, display equipment, monitoring equipment and the like.
The optical glass has the properties of excellent chemical stability, lower refractive index temperature coefficient and the like, and is particularly suitable for being applied to the fields of vehicle-mounted monitoring and security protection and the like.
Examples
< example of optical glass >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having optical glass compositions shown in tables 1 to 2 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2. Wherein Al is2O3/B2O3Is denoted by K1; al (Al)2O3/SiO2Is denoted by K2; la2O3/Y2O3Is denoted by K3; the CaO/MgO value is expressed as K4; (Na)2O+K2O)/Li2The value of O is denoted by K5.
TABLE 1
TABLE 2
< glass preform example >
Various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens and a plano-concave lens, and preforms such as prisms were produced from the glasses obtained in examples 1 to 20 of optical glass by means of polishing or press molding such as reheat press molding and precision press molding.
< optical element example >
The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.
< optical Instrument example >
The optical element obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.
Claims (16)
1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 22：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3: 10 to 45% of Al2O3/B2O30.5 to 4.0.
2. An optical glass according to claim 1, characterised in that it further comprises, in percentages by weight: ZrO (ZrO)2: 0-8%, and/or MgO: 0 to 8%, and/or P2O5: 0 to 5%, and/or Gd2O3: 0 to 10%, and/or TiO2: 0 to 10%, and/or Nb2O5: 0-5%, and/or ZnO: 0-10%, and/or CaO: 0-8%, and/or SrO + BaO: 0 to 8%, and/or Li2O: 0 to 4%, and/or Na2O: 0 to 4%, and/or K2O: 0-4%, and/or a clarifying agent: 0 to 2 percent.
3. Optical glass, characterized in that its composition, expressed in weight percentage, is represented by SiO2：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3：10～45％、ZrO2：0～8％、MgO：0～8％、P2O5：0～5％、Gd2O3：0～10％、TiO2：0～10％、Nb2O5：0～5％、ZnO：0～10％、CaO：0～8％、SrO+BaO：0～8％、Li2O：0～4％、Na2O：0～4％、K2O: 0-4% of a clarifying agent: 0 to 2% of Al2O3/B2O30.5 to 4.0.
4. An optical glass characterized by containing SiO2、B2O3、Al2O3、R2O3And RO, wherein Al2O3/B2O30.5 to 4.0, the refractive index n of the optical glassd1.65-1.78, Abbe number vd49 to 56, coefficient of thermal expansion α100/300℃Is 75X 10-7below/K, said R2O3Is La2O3、Y2O3、Gd2O3R0 is one or more of MgO, CaO, SrO and BaO.
5. An optical glass according to claim 4, characterised in that its composition, expressed in weight percentage, contains: SiO 22：10～30％、B2O3：5～20％、Al2O3：10～35％、La2O3：15～40％、Y2O3：10～45％、ZrO2：0～8％、MgO：0～8％、P2O5：0～5％、Gd2O3：0～10％、TiO2：0～10％、Nb2O5：0～5％、ZnO：0～10％、CaO：0～8％、SrO+BaO：0～8％、Li2O：0～4％、Na2O：0～4％、K2O: 0-4% of a clarifying agent: 0 to 2 percent.
6. An optical glass according to any one of claims 1 to 5, wherein the composition, expressed in weight percent, satisfies one or more of the following 5 conditions:
1)Al2O3/B2O30.7 to 3.5;
2)Al2O3/SiO20.4 to 2.0;
3)La2O3/Y2O30.5 to 2.1;
4) CaO/MgO is 0-1.2;
5)(Na2O+K2O)/Li2o is 0 to 1.1.
7. An optical glass according to any one of claims 1 to 5, comprising, in weight percent: SiO 22: 12-28%, and/or B2O3: 7 to 18%, and/or Al2O3: 12-30% and/or La2O3: 18 to 35%, and/or Y2O3: 13 to 40%, and/or ZrO2: 0.5-6%, and/or MgO: 0.5 to 6%, and/or P2O5: 0 to 3%, and/or Gd2O3: 0 to 5%, and/or TiO2: 0 to 5%, and/or Nb2O5: 0-3%, and/or ZnO: 0.5-8%, and/or CaO: 0-6%, and/or SrO + BaO: 0 to 4%, and/or Li2O: 0 to 3%, and/or Na2O: 0 to 3%, and/or K2O: 0-3%, and/or a clarifying agent: 0 to 1 percent.
8. An optical glass according to any one of claims 1 to 5, wherein the composition, expressed in weight percent, satisfies one or more of the following 5 conditions:
1)Al2O3/B2O30.8 to 3.0;
2)Al2O3/SiO20.5 to 1.8;
3)La2O3/Y2O30.6 to 1.9;
4) CaO/MgO is 0-1.0;
5)(Na2O+K2O)/Li2o is 0 to 1.0.
9. An optical glass according to any one of claims 1 to 5, comprising, in weight percent: SiO 22: 14 to 25%, and/or B2O3: 9 to 16% and/or Al2O3: 14 to 22%, and/or La2O3: 20 to 30%, and/or Y2O3: 15 to 35%, and/or ZrO2: 0.5-4%, and/or MgO: 0.5-4%, and/or ZnO: 0.5-5%, and/or CaO: 0 to 3%, and/or Li2O: 0.1-2%, and/or a clarifying agent: 0 to 0.5 percent.
10. An optical glass according to any one of claims 1 to 5, wherein the composition, expressed in weight percent, satisfies one or more of the following 4 conditions:
1)Al2O3/SiO20.7 to 1.4;
2)La2O3/Y2O30.7 to 1.7;
3) CaO/MgO is 0-0.8;
4)(Na2O+K2O)/Li2o is 0 to 0.8.
11. The method according to any one of claims 1 to 5Optical glass characterized in that it does not contain P in its composition2O5And/or does not contain Gd2O3And/or does not contain TiO2And/or no Nb2O5And/or does not contain BaO, and/or does not contain SrO, and/or does not contain K2O, and/or does not contain Na2O。
12. The optical glass according to any one of claims 1 to 5, wherein the refractive index n of the optical glassd1.65 to 1.78, preferably 1.68 to 1.74; abbe number vd49 to 56, preferably 50 to 54.
13. The optical glass according to any one of claims 1 to 5, wherein the optical glass has an acid-resistance stability DAIs more than 3 types, and preferably has acid resistance stability DAIs more than 2 types; and/or a temperature coefficient of refractive index dn/dt of 10.0 x 10-6A temperature coefficient of refractive index dn/dt of 9.0X 10 is preferably not more than/° C-6A temperature coefficient of refractive index dn/dt of 8.5X 10 or less-6A temperature coefficient of refractive index dn/dt of 8.0X 10 or less-6Below/° c; and/or lambda80Is less than or equal to 405nm, preferably lambda80Is less than or equal to 400nm, more preferably lambda80Is less than or equal to 395 nm; and/or Knoop hardness HKIs 680 x 107Pa or more, preferably Knoop hardness HKIs 685 × 107Pa or more, more preferably Knoop hardness HKIs 690X 107Pa or more, and/or a coefficient of thermal expansion α100/300℃Is 75X 10-7below/K, the thermal expansion coefficient is preferably α100/300℃Is 73X 10-7A thermal expansion coefficient of α or less is more preferable100/300℃Is 70X 10-7and/K is less than or equal to.
14. A glass preform made of the optical glass according to any one of claims 1 to 13.
15. An optical element produced from the optical glass according to any one of claims 1 to 13 or the glass preform according to claim 14.
16. An optical device comprising the optical glass according to any one of claims 1 to 13 or the optical element according to claim 15.
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| CN111533443A (en) * | 2020-05-27 | 2020-08-14 | 成都光明光电股份有限公司 | Optical glass |
| CN111574049A (en) * | 2020-05-27 | 2020-08-25 | 成都光明光电股份有限公司 | Glass composition |
| CN111533443B (en) * | 2020-05-27 | 2022-04-15 | 成都光明光电股份有限公司 | Optical glass |
| CN111977969A (en) * | 2020-08-31 | 2020-11-24 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
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| CN112047625B (en) * | 2020-09-17 | 2022-04-15 | 成都光明光电股份有限公司 | Ultraviolet-transmitting optical glass |
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