CN111170631A - Heavy lanthanum flint glass - Google Patents
Heavy lanthanum flint glass Download PDFInfo
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- CN111170631A CN111170631A CN202010095951.7A CN202010095951A CN111170631A CN 111170631 A CN111170631 A CN 111170631A CN 202010095951 A CN202010095951 A CN 202010095951A CN 111170631 A CN111170631 A CN 111170631A
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Abstract
The invention provides heavy lanthanum flint glass with refractive index of 1.82-1.87, Abbe number of 30-35, and no obvious crystallization on the surface, which is maintained at Tg +230 ℃ for more than 30 minutes, and the composition of the heavy lanthanum flint glass contains LnO expressed by mole percentage of oxide2(LnO2Is SiO2、TiO2、ZrO2、GeO2、CeO2One or more of) M2O3(M2O3Is B2O3、La2O3、Y2O3、Yb2O3、Gd2O3、Ga2O3、Bi2O3、Al2O3、Sb2O3One or more of) D)2O5(D2O5Is Nb2O5、Ta2O5、P2O5One or more of), RO. The invention relates to aThe reasonable component proportion design is suitable for manufacturing large-numerical aperture optical fibers and glass elements needing to be subjected to multiple heat treatments under the condition of ensuring the expected optical performance index.
Description
The application is a divisional application of an invention patent application with the application number of 201610801517.X, the application date of 2016, 9, month and 5, and the name of "heavy lanthanum flint glass".
Technical Field
The invention relates to high-refraction glass, in particular to flint glass with the refractive index of 1.82-1.87 and the Abbe number of 30-35, which has high transmittance in ultraviolet to visible wave bands and has excellent anti-crystallization performance in the reheating shaping process.
Background
The glass with the refractive index of 1.82-1.87 and the Abbe number of 30-35 belongs to lanthanum flint glass with high refractive index, and is widely applied to various optical systems due to high refractive index and low dispersion, thereby being an important optical base material. In the past, such glasses have generally been used to make lenses in lenses. The mainstream technology for manufacturing the lens at present adopts a secondary compression method to manufacture a lens blank, and then the lens blank is polished to obtain a qualified glass lens. The "secondary press" processing technology of optical glass is that the blank glass is cut into small blocks, heated to the temperature near the softening temperature of the glass (generally about Tg +230 ℃) in a furnace body, then the glass is put into a mould, and pressed under the action of external force to obtain a proper lens shape. In the heating process of the glass, the temperature of Tg +230 ℃ of the glass is generally in the recrystallization temperature range of heavy lanthanum flint glass, and if the devitrification resistance of the glass is poor, surface and internal devitrification can be formed in the secondary pressing process, so that pressed parts are scrapped. Therefore, in the component design of the heavy lanthanum flint glass, the devitrification resistance of the glass needs to be considered and optimized. Generally, the heavy lanthanum flint glass with the optical performance does not have obvious crystallization on the surface under the condition that the Tg is plus 230 ℃ and the temperature is kept for 15 minutes, and the crystallization resistance of the heavy lanthanum flint glass can meet the requirement of secondary compression. Therefore, the commercially available heavy lanthanum flint glass with the refractive index of 1.82-1.87 and the Abbe number of 30-35 generally meets the requirement that the surface does not have obvious crystallization after the temperature is maintained for 15 minutes at Tg +230 ℃. However, it is difficult to achieve devitrification resistance without significant surface devitrification on the glass at Tg +230 ℃ for 30 minutes due to cost and balance of other properties.
In some special applications, however, it is desirable to have a glass with a better devitrification resistance near the softening temperature. For example, for large numerical aperture fibers, higher index glasses are required. For the optical fiber, the larger the refractive index difference between the core and the cladding glass is, the larger the numerical aperture value of the optical fiber is, and the stronger the light-collecting capability is. For example: in Zhou Dechun et al, "preparation of large-numerical-aperture image-transmitting optical fiber and research on optical performance," progress in laser and optoelectronics, 47,120605(2010) ", an optical fiber was described in which a crown glass having a refractive index of 1.51 was used as a cladding and a glass having a refractive index of 1.74 was used as a core, and the numerical aperture of the optical fiber was 0.8725. In the fields of medical optical fiber endoscopes and industrial automatic detection equipment which are developed vigorously at present, optical fibers with larger numerical aperture are needed, and core layer glass with higher refractive index is also needed. The refractive index and the transmittance of the heavy lanthanum flint glass can meet the requirement of the optical fiber core layer glass with larger numerical aperture. However, at present, most of heavy lanthanum flint glass is applied to lenses, and the crystallization performance of the heavy lanthanum flint glass meets the requirement of a secondary compression process, and generally meets the requirement of Tg +230 ℃ heat preservation for 15 minutes. However, in the process of drawing an optical fiber, the high refractive index glass rod as a raw material needs to be kept at the temperature of Tg +230 ℃ for 30 minutes, even 45 minutes, and the surface does not have obvious crystallization, so that the drawing requirement of the glass optical fiber can be met.
With the development of optical equipment, more and more special-shaped parts appear, and the glass needs to be pressed successfully by 2 times or even 3 times of 'secondary pressing' process. If the devitrification resistance of the glass cannot meet the higher devitrification resistance requirement, the glass is only manufactured in a cold working mode, and the manufacturing cost is greatly increased. In addition, the defective products of the heavy lanthanum flint glass in the secondary pressing process can only be discarded as waste materials or melted back into the furnace to be melted into the glass, the reason is that the surface of the heavy lanthanum flint glass is devitrified and scrapped after undergoing the primary secondary pressing process, and the basic reason is that the devitrification resistance of the glass is not enough and the requirement of multiple heating and pressing processes cannot be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing the heavy lanthanum flint glass which has the refractive index of 1.82-1.87, the Abbe number of 30-35, the requirement of keeping for more than 30 minutes at the temperature of Tg +230 ℃ and no obvious crystallization on the surface.
The present invention solves the technical problemThe technical scheme adopted by the subject is as follows: heavy lanthanum flint glass, the composition of which contains LnO in mole percent2(LnO2Is SiO2、TiO2、ZrO2、GeO2、CeO2One or more of) M2O3(M2O3Is B2O3、La2O3、Y2O3、Yb2O3、Gd2O3、Ga2O3、Bi2O3、Al2O3、Sb2O3One or more of) D)2O5(D2O5Is Nb2O5、Ta2O5、P2O5One or more of the above-mentioned materials), RO (RO is one or more of ZnO, BaO, SrO, CaO and MgO), its refractive index is 1.82-1.87, Abbe number is 30-35, and the glass can be kept at Tg +230 deg.C for above 30 min, and its surface does not produce obvious crystallization.
Further, the composition comprises, expressed in mole percent on an oxide basis: SiO 2225-50％、B2O32-10％、TiO210-20％、ZnO 4-16％、ZrO22-10％、La2O33-12％、Nb2O51-8％、BaO 10-30％。
Heavy lanthanum flint glass, the composition of which comprises, expressed in mole percent on an oxide basis: SiO 2225-50％、B2O32-10％、TiO210-20％、ZnO 4-16％、ZrO22-10％、La2O33-12％、Nb2O51-8％、BaO 10-30％。
Further, the method also comprises the following steps: 0-5% of SrO, 0-4% of CaO, 0-4% of MgO and Li2O+Na2O+K2O0-2％、Sb2O30-0.5％。
The heavy lanthanum flint glass comprises the following components in percentage by mole of oxides: SiO 2225-50％、B2O32-10％、TiO210-20％、ZnO 4-16％、ZrO22-10％、La2O33-12％、Nb2O51-8％、BaO 10-30％、SrO 0-5％、CaO 0-4％、MgO 0-4％、Li2O+Na2O+K2O 0-2％、Sb2O30-0.5％。
Further, wherein: SiO 2230 to 45 percent; and/or B2O33 to 9 percent; and/or TiO212 to 19 percent; and/or ZnO 6-14%; and/or ZrO23 to 8 percent; and/or La2O34 to 10 percent; and/or Nb2O52 to 7 percent; and/or BaO 12-25%; and/or SrO 0-3%; and/or 0-2% of CaO; and/or MgO 0-2%; and/or Sb2O30-0.3％。
Further, wherein: SiO 2232-43%; and/or B2O34 to 8 percent; and/or TiO213 to 17 percent; and/or ZnO 6-12%; and/or ZrO24 to 7 percent; and/or La2O35 to 9 percent; and/or Nb2O52 to 5 percent; and/or BaO 14-20%.
Further, wherein: does not contain Ta2O5(ii) a And/or does not contain WO3(ii) a And/or does not contain Y2O3(ii) a And/or does not contain Ga2O3(ii) a And/or does not contain GeO2。
Further, wherein: SiO 22/B2O3Is greater than or equal to 3; and/or BaO/(TiO)2+ZnO+ZrO2) The ratio of (A) to (B) is 0.4-1.3; and/or TiO2/Nb2O5The ratio of (A) to (B) is 3-9.
Further, wherein: SiO 22/B2O3Is greater than or equal to 4; and/or BaO/(TiO)2+ZnO+ZrO2) The ratio of (A) to (B) is 0.45-1; and/or TiO2/Nb2O5The ratio of (A) to (B) is 4-8.
Further, wherein: SiO 22/B2O3Is greater than or equal to 5; and/or BaO/(TiO)2+ZnO+ZrO2) The ratio of (A) to (B) is 0.5-0.8; and/or TiO2/Nb2O5The ratio of (A) to (B) is 4.5-7.5.
Further, wherein: the glass is kept for more than 30 minutes at the temperature of Tg +230 ℃, obvious crystallization does not occur on the surface, the refractive index is 1.82-1.87, and the Abbe number is 30-35.
Further, wherein: a value of τ 400nm (10mm) greater than or equal to 70%.
Further, wherein: the glass is kept at the temperature of Tg +230 ℃ for more than 45 minutes, and obvious crystallization on the surface does not occur.
The glass preform is made of the optical glass.
The optical element is made of the optical glass.
The optical fiber is made of the optical glass.
The invention has the beneficial effects that: through reasonable component proportion design, the optical glass has higher transmittance under the condition of ensuring the expected optical performance index; the glass is insulated for more than 30 minutes at the temperature of Tg +230 ℃, has no obvious crystallization on the surface, and is suitable for manufacturing large-numerical aperture optical fibers and glass elements needing to be subjected to multiple heat treatments.
Detailed Description
The individual components of the glass according to the invention will be described below, the contents of the individual components being expressed in mol% unless otherwise stated.
In the glass of the invention, SiO2Is a network former of glass and is a main component constituting a glass skeleton. SiO 22The content is closely related to the devitrification resistance, transmittance, refractive index and dispersion of the glass. If the content is less than 25 percent, the refractive index and the dispersion of the glass cannot reach the design expectation, and meanwhile, the anti-crystallization performance and the transmittance of the glass are greatly reduced; if the content is more than 50%, the solubility and devitrification resistance of the glass may be deteriorated, and the refractive index and dispersion may not be as designed. Therefore, in the present invention, SiO2The content of (B) is set to 25 to 50%, preferably 30 to 45%, and more preferably 32 to 43%.
B2O3Also one of the glass formers, to which glass B is added in a suitable amount2O3Can make the skeleton structure of the glass more compact and improve the glassTransmittance, devitrification resistance, and glass dissolution properties. If B is2O3The content is higher than 10%, the devitrification resistance and the transmittance of the glass can be reduced; if the content is less than 2%, the glass is easily devitrified, the raw materials are slowly dissolved, and the devitrification resistance of the glass is rapidly reduced. Thus, B2O3The content of (B) is set to 2 to 10%, preferably 3 to 9%, and more preferably 4 to 8%.
SiO2And B2O3All are network formers of glass, but the structures formed in the glass are not consistent, and the proportional relationship of the two network formers is closely related to the internal structure of the glass. That is, in the bulk system glass, SiO2And B2O3The proportional relation of the glass has close relation with the anti-crystallization performance, the glass forming performance, the transmittance and other performances of the glass. The inventor confirms through experiments that when SiO2/B2O3When the ratio of (A) to (B) is 3 or more, preferably 4 or more, and more preferably 5 or more, the devitrification resistance and transmittance of the glass are optimum. In addition, from the viewpoint of production process, when SiO is used2/B2O3When the ratio of (A) to (B) meets the value, the glass has little erosion to the ceramic crucible in the dissolving stage, so that the glass can be dissolved without a platinum crucible in the material melting stage, the content of platinum element in the glass is greatly reduced, the transmittance of the glass can be further improved, and the risk of producing platinum inclusions is reduced.
La2O3The oxide is a high-refraction low-dispersion oxide, and can improve the refractive index of the glass and adjust the dispersion when added into the glass. In the present invention, La2O3If the content of (A) is less than 3%, the refractive index and dispersion of the glass cannot meet the design requirements; if the content is more than 12%, devitrification resistance of the glass is rapidly deteriorated. Therefore, the content thereof is set to 3 to 12%, preferably 4 to 10%, and more preferably 5 to 9%.
ZrO2The oxide is a high-refraction low-dispersion oxide, and can improve the refractive index of the glass and adjust the dispersion when added into the glass. At the same time, an appropriate amount of ZrO2Added into the glass, the devitrification resistance of the glass can be improvedCan be blended into glass with stability. In the invention, if the content is less than 2%, the anti-devitrification performance and the glass forming stability of the glass are not obviously improved; if the content is more than 10%, the glass becomes difficult to melt, the melting temperature increases, and inclusions in the glass and the transmittance thereof are liable to decrease. Therefore, the content thereof is set to 2 to 10%, preferably 3 to 8%, and more preferably 4 to 7%.
Nb2O5The glass is a high-refractive-index and high-dispersion oxide, and the refractive index and the dispersion of the glass can be improved by adding the oxide into the glass. Especially, the glass contains a large amount of TiO2When the components are added, a small amount of Nb is added2O5Can enhance the devitrification resistance of the glass and improve the transmittance of the glass. If the content is less than 1%, the effect of improving the anti-crystallization performance and the transmittance is not obvious; if the content is more than 8%, the refractive index and dispersion of the glass cannot meet the design requirements, and the cost of the glass rapidly rises. Therefore, the content thereof is limited to 1 to 8%, preferably 2 to 7%, and more preferably 2 to 5%.
TiO2The glass is a high-refraction high-dispersion oxide, and the refractive index and the dispersion of the glass can be improved by adding the oxide into the glass. At the same time, a suitable amount of TiO2When the glass is added into glass, the glass can enter a glass network to become a part of the glass network, and the stability, particularly the devitrification resistance, of the glass is improved. TiO 22The addition of Nb into glass can reduce the relatively high-price Nb2O5The amount of (2) can reduce the raw material cost of the glass. But if too much TiO2When the glass is added, firstly, the refractive index and the dispersion of the glass are higher than the expected refractive index and secondly, the transmittance of the glass is greatly deteriorated, and the stability and the anti-devitrification performance of the glass cannot reach the expected refractive index and dispersion of the glass. If TiO2Too little, the refractive index and dispersion of the glass may be lower than expected by design, and the devitrification resistance of the glass may be reduced. Thus TiO2The content of (B) is set to 10 to 20%, preferably 12 to 19%, and more preferably 13 to 17%.
Further, TiO2And Nb2O5All belong to high-refraction high-dispersion oxides, and can improve the refractive index, dispersion and crystallization resistance of the glass when added into the glassStability of the glass. The research of the inventor finds that the TiO2And Nb2O5The addition ratio of (A) has a close relationship with the devitrification resistance and the glass stability of the glass. In the glass of the invention, when TiO2/Nb2O5When the ratio of (A) to (B) is in the range of 3 to 9, more preferably 4 to 8, still more preferably 4.5 to 7.5, the devitrification resistance of the glass, the transmittance of the glass and the stability of the glass are optimum.
ZnO is added into the glass of the system, so that the refractive index and dispersion of the glass can be adjusted, the devitrification resistance of the glass is improved, and the stability of the glass is improved. ZnO can also reduce the high-temperature viscosity of the glass, so that the glass can be smelted at a lower temperature, and the transmittance of the glass can be improved. If the content of the glass is less than 4 percent, the effects of improving the crystallization resistance of the glass, enhancing the stability of the glass and reducing the high-temperature viscosity of the glass are not obvious; if the content is more than 16%, devitrification resistance of the glass at the time of molding and processing is drastically deteriorated. Therefore, the content thereof is limited to 4 to 16%, preferably 6 to 14%, and more preferably 6 to 12%.
BaO, SrO, CaO and MgO belong to alkaline earth metal oxides, and the addition of BaO, SrO, CaO and MgO into the glass can adjust the refractive index and dispersion of the glass and enhance the stability of the glass, particularly the stability of devitrification resistance. In addition, the addition of an appropriate amount of alkaline earth metal oxide is advantageous for the enhancement of the glass transmittance. Excessive addition of alkaline earth metal oxides can lead to unexpected refractive index, dispersion, weather resistance and devitrification resistance of the glass; too little alkaline earth metal oxide causes a sharp decrease in devitrification resistance, transmittance and stability of the glass.
In the glass of the present invention, the above four alkaline earth metal oxides may be added, but because of differences in the respective properties of the above four alkaline earth metal oxides, especially in the influence on the devitrification resistance of the glass, when selecting the alkaline earth metal oxide, BaO and SrO are preferably selected, which is more advantageous in improving the devitrification resistance of the glass than the other two alkaline earth metal oxides. However, since the raw material cost of SrO is much higher than BaO, BaO is preferably used as the alkaline earth metal oxide in the present system glass in view of the performance and cost. The BaO content is limited to 10 to 30%, preferably 12 to 25%, and more preferably 14 to 20%.
Further, the inventor's experiments confirmed that when SiO is contained in the glass2And B2O3When the content of (B) is in the above range, the glass has transmittance and devitrification resistance in combination with BaO and TiO2、ZnO、ZrO2The components have close synergistic relationship. When BaO/(TiO) is satisfied2+ZnO+ZrO2) The value of (A) is 0.4 to 1.3, preferably 0.45 to 1, and more preferably 0.5 to 0.8, and the transmittance and devitrification resistance of the glass are optimum.
In the present invention, the SrO content is limited to 0 to 5%, preferably 0 to 3%, and more preferably not added. The CaO content is limited to 0 to 4%, preferably 0 to 2%, and more preferably not added. The MgO content is limited to 0 to 4%, preferably 0 to 2%, and more preferably not added.
Li2O、Na2O、K2O belongs to alkali metal oxide, and the small amount of O added into glass can improve the melting performance and bubble quality of the glass and lower the softening temperature of the glass. Therefore, in the present invention, Li2O、Na2O、K2O may be added singly or in combination of two or three, but if the total amount exceeds 2%, the devitrification resistance of the glass is drastically lowered. Thus Li2O、Na2O、K2The total amount of O is not more than 2%, and preferably no addition is made.
Sb2O3The refining agent is added into the glass to facilitate bubble elimination, but if the adding amount exceeds 1 percent, more platinum inclusions are generated in the glass during smelting, and the short-wave transmittance of the glass is reduced. Therefore, in the present invention, the content is limited to 0 to 0.5%, preferably 0 to 0.3%, and more preferably not added.
In the present invention, Ta is preferably not contained for the purpose of reducing the production cost2O5、WO3、Y2O3、Ga2O3And GeO2And the like.
The properties of the optical glass of the present invention will be described below:
the refractive index and Abbe number are tested according to the method specified in GB/T7962.1-2010.
The internal transmission at 400nm of a 10mm thick sample, τ 400nm (10mm), was measured according to the method specified in GB/T7962.12-2010.
The Tg temperature of the glass was measured using the method specified in GB/T7962.16-2010.
The method for testing the devitrification resistance of the glass comprises the following steps: cutting sample glass into a specification of 20 multiplied by 10mm, placing the sample glass into a muffle furnace with the temperature of Tg +230 ℃ for heat preservation for a preset time, taking out the sample glass, placing the sample glass into heat preservation cotton for slow cooling, and observing the surface crystallization condition after cooling.
Through tests, the optical glass of the invention has the following properties: the refractive index is 1.82-1.87, and the Abbe number is 30-35; an internal transmittance τ 400nm (10mm) of 70% or more at a wavelength of 400 nm; cutting the sample glass into a specification of 20 multiplied by 10mm, putting the sample glass into a muffle furnace with the temperature of Tg +230 ℃ for heat preservation for 30 minutes, preferably for 45 minutes, taking the sample glass out, putting the sample glass into heat preservation cotton for slow cooling, and ensuring that no obvious crystallization exists on the surface. The surface of the invention without obvious crystallization refers to that: the surface has no crystallization spots or crystallization spots, but the area of the surface accounts for less than 5 percent of the whole area and the crystallization depth does not exceed 0.5 mm.
In order to further understand the technical solution of the present invention, examples of the optical glass of the present invention will be described below. It should be noted that these examples do not limit the scope of the present invention.
The optical glasses (examples 1 to 20) shown in tables 1 to 2 were obtained by weighing and mixing general raw materials (such as oxides, hydroxides, carbonates, nitrates, etc.) for optical glasses in the ratios of the respective examples shown in the tables, placing the mixed raw materials in a platinum crucible, melting at 1350 to 1400 ℃ for 2.5 to 4 hours, and after fining, stirring and homogenizing, obtaining a homogeneous molten glass free from bubbles and containing no undissolved substances, casting this molten glass in a mold and annealing.
Compositions and refractive indices (nd), Abbe numbers (vd), internal transmittances at 400nm wavelength (. tau.400 nm), SiO of examples 1-20 of the present invention2/B2O3Is denoted by K1; BaO/(TiO)2+ZnO+ZrO2) Value of (A)Denoted by K2; TiO 22/Nb2O5Is denoted by K3; the sample glass was cut into a size of 20X 10mm, placed in a muffle furnace at a temperature of Tg +230 ℃ for 45 minutes, taken out, placed in heat-insulating cotton for slow cooling, cooled, and observed for surface devitrification, as indicated by K4. No obvious crystallization is marked as "A", and obvious crystallization is marked as "B".
TABLE 1
TABLE 2
| mol％ | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| SiO2 | 38.60 | 37.10 | 38.30 | 38.60 | 38.00 | 38.00 | 37.00 | 38.60 | 34.10 | 38.60 |
| B2O3 | 5.00 | 3.90 | 5.00 | 5.00 | 5.60 | 5.00 | 4.00 | 7.00 | 4.10 | 5.00 |
| TiO2 | 15.00 | 16.20 | 15.60 | 15.20 | 15.20 | 15.20 | 13.00 | 14.00 | 12.80 | 15.20 |
| ZnO | 7.90 | 7.90 | 8.00 | 8.10 | 8.10 | 8.10 | 4.50 | 10.00 | 15.90 | 7.00 |
| La2O3 | 7.40 | 8.80 | 7.30 | 7.40 | 7.40 | 5.40 | 7.00 | 6.80 | 7.50 | 7.40 |
| ZrO2 | 5.40 | 5.30 | 4.80 | 5.40 | 5.40 | 5.40 | 4.00 | 5.40 | 6.50 | 6.40 |
| Nb2O5 | 3.20 | 3.20 | 3.20 | 3.20 | 3.20 | 3.00 | 3.00 | 3.20 | 1.70 | 3.00 |
| BaO | 16.00 | 16.60 | 16.80 | 16.10 | 17.10 | 19.90 | 27.50 | 15.00 | 17.40 | 17.40 |
| CaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 1.50 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Li2O+Na2O+K2O | 0.00 | 0.00 | 1.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Sb2O3 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Total up to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| K1 | 7.72 | 9.51 | 7.66 | 7.72 | 6.79 | 7.60 | 9.25 | 5.51 | 8.32 | 7.72 |
| K2 | 0.57 | 0.56 | 0.59 | 0.56 | 0.60 | 0.69 | 1.28 | 0.51 | 0.47 | 0.61 |
| K3 | 4.69 | 5.06 | 4.88 | 4.75 | 4.75 | 5.07 | 4.33 | 4.38 | 7.53 | 5.07 |
| Nd | 1.84674 | 1.86560 | 1.85011 | 1.84723 | 1.85058 | 1.83010 | 1.84290 | 1.83099 | 1.82288 | 1.84529 |
| Vd | 32.44 | 31.21 | 32.22 | 32.10 | 32.34 | 34.01 | 33.70 | 32.97 | 33.95 | 32.40 |
| Tg | 695 | 690 | 670 | 670 | 695 | 685 | 685 | 680 | 670 | 695 |
| τ400nm(％) | 74.5 | 73.6 | 76.2 | 75.4 | 74.5 | 83.7 | 80.1 | 78.8 | 82.7 | 71.1 |
| K4 | A | A | A | A | A | A | A | A | A | A |
Claims (17)
1. Heavy lanthanum flint glass, characterized in that its composition comprises, expressed in terms of mole percentage of oxides, LnO2(LnO2Is SiO2、TiO2、ZrO2、GeO2、CeO2One or more of) M2O3(M2O3Is B2O3、La2O3、Y2O3、Yb2O3、Gd2O3、Ga2O3、Bi2O3、Al2O3、Sb2O3One or more of) D)2O5(D2O5Is Nb2O5、Ta2O5、P2O5One or more of the above-mentioned materials), RO (RO is one or more of ZnO, BaO, SrO, CaO and MgO), its refractive index is 1.82-1.87, Abbe number is 30-35, and the glass can be kept at Tg +230 deg.C for above 30 min, and its surface does not produce obvious crystallization.
2. The heavy lanthanum flint glass according to claim 1, wherein the composition comprises, in mole percent on an oxide basis: SiO 2225-50％、B2O32-10％、TiO210-20％、ZnO 4-16％、ZrO22-10％、La2O33-12％、Nb2O51-8％、BaO 10-30％。
3. Heavy lanthanum flint glass is characterized in that the composition thereof comprises, expressed in terms of mole percentages of oxides: SiO 2225-50％、B2O32-10％、TiO210-20％、ZnO 4-16％、ZrO22-10％、La2O33-12％、Nb2O51-8％、BaO 10-30％。
4. The heavy lanthanum flint glass of claim 2 or 3, further comprising: 0-5% of SrO, 0-4% of CaO, 0-4% of MgO and Li2O+Na2O+K2O 0-2％、Sb2O30-0.5％。
5. The heavy lanthanum flint glass is characterized by comprising the following components in percentage by mole of oxides: SiO 2225-50％、B2O32-10％、TiO210-20％、ZnO 4-16％、ZrO22-10％、La2O33-12％、Nb2O51-8％、BaO 10-30％、SrO 0-5％、CaO 0-4％、MgO 0-4％、Li2O+Na2O+K2O 0-2％、Sb2O30-0.5％。
6. The heavy lanthanum flint glass of any of claims 1-5, wherein: SiO 2230 to 45 percent; and/or B2O33 to 9 percent; and/or TiO212 to 19 percent; and/or ZnO 6-14%; and/or ZrO23 to 8 percent; and/or La2O34 to 10 percent; and/or Nb2O52 to 7 percent; and/or BaO 12-25%; and/or SrO 0-3%; and/or 0-2% of CaO; and/or MgO 0-2%; and/or Sb2O30-0.3％。
7. The heavy lanthanum flint glass of any of claims 1-5, wherein: SiO 2232-43%; and/or B2O34 to 8 percent; and/or TiO213 to 17 percent; and/or ZnO 6-12%; and/or ZrO24-7％；And/or La2O35 to 9 percent; and/or Nb2O52 to 5 percent; and/or BaO 14-20%.
8. The heavy lanthanum flint glass of any of claims 1-4, wherein: does not contain Ta2O5(ii) a And/or does not contain WO3(ii) a And/or does not contain Y2O3(ii) a And/or does not contain Ga2O3(ii) a And/or does not contain GeO2。
9. The heavy lanthanum flint glass of any of claims 1-5, wherein: SiO 22/B2O3Is greater than or equal to 3; and/or BaO/(TiO)2+ZnO+ZrO2) The ratio of (A) to (B) is 0.4-1.3; and/or TiO2/Nb2O5The ratio of (A) to (B) is 3-9.
10. The heavy lanthanum flint glass of any of claims 1-5, wherein: SiO 22/B2O3Is greater than or equal to 4; and/or BaO/(TiO)2+ZnO+ZrO2) The ratio of (A) to (B) is 0.45-1; and/or TiO2/Nb2O5The ratio of (A) to (B) is 4-8.
11. The heavy lanthanum flint glass of any of claims 1-5, wherein: SiO 22/B2O3Is greater than or equal to 5; and/or BaO/(TiO)2+ZnO+ZrO2) The ratio of (A) to (B) is 0.5-0.8; and/or TiO2/Nb2O5The ratio of (A) to (B) is 4.5-7.5.
12. The heavy lanthanum flint glass of any of claims 3-5, wherein: the glass is kept for more than 30 minutes at the temperature of Tg +230 ℃, obvious crystallization does not occur on the surface, the refractive index is 1.82-1.87, and the Abbe number is 30-35.
13. The heavy lanthanum flint glass of any of claims 1-5, wherein: a value of τ 400nm (10mm) greater than or equal to 70%.
14. The heavy lanthanum flint glass of any of claims 1-5, wherein: the glass is kept at the temperature of Tg +230 ℃ for more than 45 minutes, and obvious crystallization on the surface does not occur.
15. A glass preform made of the optical glass according to any one of claims 1 to 14.
16. An optical element made of the optical glass according to any one of claims 1 to 14.
17. An optical fiber made of the optical glass according to any one of claims 1 to 14.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010095951.7A CN111170631A (en) | 2016-09-05 | 2016-09-05 | Heavy lanthanum flint glass |
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| CN201610801517.XA CN106365440A (en) | 2016-09-05 | 2016-09-05 | Dense lanthanum flint glass |
| CN202010095951.7A CN111170631A (en) | 2016-09-05 | 2016-09-05 | Heavy lanthanum flint glass |
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| CN201610801517.XA Division CN106365440A (en) | 2016-09-05 | 2016-09-05 | Dense lanthanum flint glass |
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| CN202010095951.7A Withdrawn CN111170631A (en) | 2016-09-05 | 2016-09-05 | Heavy lanthanum flint glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107140824B (en) * | 2017-07-03 | 2019-07-30 | 成都光明光电股份有限公司 | Flint optical glass with heavy lanthanum |
| WO2020017274A1 (en) * | 2018-07-18 | 2020-01-23 | 株式会社オハラ | Optical glass and optical element |
| CN111285601B (en) * | 2018-12-07 | 2022-03-08 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
| CN111285602B (en) * | 2018-12-07 | 2022-03-08 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
| CN109851217B (en) * | 2018-12-07 | 2022-03-08 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
| CN113582537B (en) * | 2021-09-07 | 2022-12-13 | 成都光明光电股份有限公司 | High-refraction high-dispersion optical glass |
| CN113735436B (en) * | 2021-09-07 | 2022-12-13 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
| CN113603367B (en) * | 2021-09-14 | 2022-12-02 | 中国建筑材料科学研究总院有限公司 | High-refractive-index glass for medium-expansion optical fiber image transmission element and preparation method thereof |
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