CN110342815B - Lanthanum flint optical glass - Google Patents
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- CN110342815B CN110342815B CN201910782347.9A CN201910782347A CN110342815B CN 110342815 B CN110342815 B CN 110342815B CN 201910782347 A CN201910782347 A CN 201910782347A CN 110342815 B CN110342815 B CN 110342815B
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- 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
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- 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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- 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
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Abstract
The invention provides a low Tg temperatureThe lanthanide glass has high short wave transmittance and strong anti-crystallization performance, and is suitable for aspheric surface precision profiling and large-caliber forming. The lanthanum flint optical glass comprises the following components in percentage by weight: SiO 222‑10％、B2O312‑25％、TiO21‑6.5％、La2O320‑45％、Y2O32‑10％、ZrO22‑7％、Nb2O55‑15％、WO31-5% and BaO 6-20%. The invention does not contain ZnO component and reduces Li through reasonable component proportion design2The content of O, the refractive index of the glass is 1.81-1.87, the Abbe number is 32-38, the Tg is lower than 630 ℃, the glass is suitable for aspheric surface precision profiling, the internal transmittance at the wavelength of 400nm is more than 87%, the devitrification resistance of the glass is A grade, no devitrification is generated in the glass, and the glass is suitable for forming large-caliber thick products.
Description
The present application is a divisional application of an invention patent application having application number 201610303608.0, application date 2016, 5, and 10 entitled "lanthanum flint optical glass".
Technical Field
The invention relates to lanthanum flint optical glass with high refraction and medium-low dispersion, in particular to optical glass with the refractive index of 1.81-1.87 and the Abbe number of 32-38.
Background
The high-refractive index medium-low dispersion lanthanum flint optical glass can improve the imaging quality of an optical instrument lens, and can be widely applied to the imaging fields of single-reflection single-power, security monitoring, vehicle-mounted video and the like. In lanthanum flint glass, especially optical glass with refractive index of 1.81-1.87 and Abbe number of 32-38, the glass component contains more TiO2、La2O3、Nb2O5The components are equal, and the absorption of light rays (corresponding to ultraviolet to blue light rays) in the wave band of 300nm-440nm is higher than that of common low-refractive-index optical glass. If the glass is applied to the optical field needing multiple reflection, after multiple absorption, even if the internal transmittances of two kinds of glass with the same refractive index and Abbe number only differ by 1%, the light quantity of the blue wave band which can finally reach the imaging device can differ by 10-30%, which brings great difficulty to the color restoration of an optical instrument. In addition, high-end imaging devices mostly use cmos as a photosensitive element, and are sensitive to blue bandIf the lens is not transparent enough to the blue band, the imaging quality of the imaging device is reduced. Therefore, how to achieve the refractive index and the Abbe number required by design through the component proportion and simultaneously improve the short-wave transmittance of the lanthanum flint glass is a hotspot of research in the field of the lanthanum flint optical glass at present.
Lanthanum flint glass, especially low Tg lanthanum flint glass applied to aspheric surface precision profiling, is easy to generate crystallization problem in the mass production process and the subsequent processing process. For current applications, particularly in the fields of earth observation, sky detection and the like, a large-caliber (diameter larger than 200mm) lens is required, and due to the characteristic that lanthanide glass is easy to crystallize in molding, the large-caliber thick-specification high-refraction lanthanide glass becomes a bottleneck of optical design.
In the mass production process of lanthanum flint glass, in order to prevent the occurrence of stripe problem, the forming temperature of the lanthanum flint glass is generally near the upper limit crystallization temperature, and then the lanthanum flint glass is discharged into a mold to be cooled into a glass blank. For lanthanum flint glass, in the initial stage of cooling, the viscosity of the glass is low, the fluidity is good, and the free migration and combination capacity of substances easy to crystallize in the components is strong. If the devitrification resistance of the glass is poor and the time for the glass to cool from the liquid state to the solid state is long, it will provide sufficient devitrification time for the devitrification susceptible material to form crystalline nuclei or even macroscopic crystals within the glass. Particularly, in the process of forming large-caliber and thick-specification products of the high-refraction lanthanide glass, the molten glass is a poor thermal conductor, the cooling condition is poor, and the crystallization is particularly easy in the central part of poor glass cooling and the three-phase interface with a lower crystallization threshold. For lanthanum flint glass, especially for aspheric surface precision compression type low softening point lanthanum flint glass, how to match glass components to improve the anti-crystallization performance of the glass in the cooling process is of great significance for reducing the production difficulty, especially the process difficulty of large-caliber thick-specification products.
In addition, in the process of reheating and shaping the glass, if the devitrification resistance of the glass is poor, a thicker devitrification layer is easily formed on the surface of a workpiece, or devitrification particles are formed inside the workpiece, so that the product is scrapped. According to practical experience in the aspect of pressing, the devitrification resistance of the glass is more than B level, the difficulty of the secondary pressing process is low, and the yield is high.
CN201410408995.5 describes an optical glass whose composition contains 0.5 to 22 mol% of ZnO. High ZnO content results in longer glass frit properties, slower solidification during the forming cooling process, and easy internal crystallization especially during the large-caliber forming process. In addition, when the high content ZnO glass is smelted by using a platinum crucible, if the atmosphere control is not good, the platinum crucible is easy to damage, which brings limitation to the production process.
CN200910063091.2 describes an optical glass which uses 2 to 8% by weight of Li2O is used for reducing the Tg temperature of the glass, thus reducing the devitrification resistance of the glass and being difficult to obtain large-caliber products. At the same time, a high content of Li2O-glass risks contaminating the mold during precision profiling.
Disclosure of Invention
The invention aims to solve the technical problem of providing the lanthanide glass which has lower Tg temperature, high short wave transmittance and strong anti-crystallization performance and is suitable for aspheric surface precision compression and large-caliber forming.
The technical scheme adopted by the invention for solving the technical problem is as follows: the lanthanum flint optical glass comprises the following components in percentage by weight: SiO 22 2-10％、B2O3 12-25％、TiO2 1-6.5％、La2O3 20-45％、Y2O3 2-10％、ZrO2 2-7％、Nb2O5 5-15％、WO3 1-5％、BaO 6-20％。
Further, the method also comprises the following steps: CaO 0-5%, SrO 0-5%, MgO 0-5%, Li2O 0-2％、K2O 0-2％、Na2O 0-3％、Sb2O3 0-1％。
Further, Li2O+K2O+Na2The total content of O is 1.5-6%.
Further, wherein SiO23-8% and/or B2O314-23% and/or TiO22-6% and/or La2O322-40% and/or Y2O33-9% and/or ZrO23-6% and/or Nb2O56-14% and/or WO31-4% and/or BaO 8-18% and/or CaO 0-3% and/or SrO 0-3% and/or MgO 0-3% and/or Li2O0.2-1% and/or K2O0.2-1% and/or Na20.5-2% of O and/or Sb2O3 0-0.5％。
Further, wherein SiO23.5-6.5% and/or B2O316-22% and/or TiO23-6% and/or La2O326-38% and/or Y2O34-8% and/or ZrO23.5-6% and/or Nb2O57-13% and/or WO32-4% and/or BaO 8-15% and/or Li2O0.2-0.8% and/or K2O0.2-0.8% and/or Na2O 0.5-1.5％。
Further, the total content of BaO + CaO + SrO + MgO is 10-16%.
Further, wherein (Li)2O+Na2O+K2O+BaO+SrO+CaO+MgO-SiO2)/TiO2Is greater than 1.
Further, wherein (La)2O3+Nb2O5)/(TiO2+Y2O3+WO3+ZrO2) Is greater than 1.
Further, the glass has a refractive index of 1.81-1.87 and an Abbe number of 32-38.
Further, the glass has Tg lower than 630 ℃, tau 400nm higher than 87% and anti-devitrification performance of A grade.
The invention has the beneficial effects that: through reasonable component proportion design, ZnO component is not contained and Li is reduced2The content of O, the refractive index of the glass is 1.81-1.87, the Abbe number is 32-38, the Tg is lower than 630 ℃, the glass is suitable for aspheric surface precision profiling, the internal transmittance at the wavelength of 400nm is more than 87%, the devitrification resistance of the glass is A grade, no devitrification is generated in the glass, and the glass is suitable for forming large-caliber thick products.
Drawings
FIG. 1 is a front view of a glass-casting mold when testing the devitrification resistance upon cooling.
Fig. 2 is a top view of fig. 1.
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% by weight unless otherwise stated.
In the glasses of the present invention, B2O3Is a main glass forming body and is a main component constituting a glass skeleton. If the content is more than 25%, the refractive index of the glass is lower than expected by design, and the chemical stability of the glass is deteriorated; if the content is less than 12%, the glass-forming property is greatly lowered and the devitrification resistance is deteriorated. Thus, in the present invention, B2O3The content of (B) is 12 to 25%, preferably 14 to 23%, and more preferably 16 to 22%.
In the glasses of the present invention, B2O3The glass is mainly composed of boron-oxygen triangle (BO)3]The structure of (a) exists, which is a loose chain-like and layered network. This is also the root cause of the poor devitrification properties of high index lanthanide glasses. SiO 22The three-dimensional network of silicon-oxygen tetrahedrons is formed in the glass, and is very compact and firm. Such networks are incorporated into glass for loose boroxine [ BO ]3]The network is consolidated so that it becomes dense. Meanwhile, the addition of a silicon-oxygen tetrahedron three-dimensional network isolates La2O3、Nb2O5The crystallization cations and the anions are subjected to equal crystallization, so that the crystallization threshold is increased, and the crystallization resistance of the glass is improved. But things always have two sides, if SiO2The content of (A) is increased without limitation, which causes difficulty in dissolution on the one hand, and on the other hand, it is inevitable to decrease B in order to maintain a high refractive index2O3Content of (A), SiO2To La2O3The solubility of (A) is extremely low, and the devitrification resistance of the glass is rapidly reduced. Therefore, if SiO is used in the present invention2The content of the glass is lower than 2 percent, the material property of the glass can be lengthened, the anti-crystallization performance is poor, and a large-caliber product is not easy to form; if the content is more than 10%, the glass needs to be melted at a higher temperature, which may cause permeationThe rate decreases. In particular with TiO in the glass2、Nb2O5When the components are equal, the excessively high melting temperature causes a sharp decrease in transmittance. In addition, too high SiO2The content of (A) also results in a decrease in the refractive index and devitrification resistance of the glass. Therefore, in the present invention, SiO2The content is limited to 2 to 10%, preferably 3 to 8%, and more preferably 3.5 to 6.5%.
BaO, SrO, CaO and MgO belong to alkaline earth metal oxides, and when the BaO, the SrO, the CaO and the MgO are added into the glass, the refractive index is improved, and simultaneously the crystallization resistance stability and the short wave transmittance of the glass can be improved.
The inventors have intensively studied and found that the addition of a certain amount of alkaline earth metal oxide in such glass system improves the devitrification resistance of the glass. The reason is that the alkaline earth metal oxides have a relatively low cationic field strength and can provide free oxygen ions when added to the glass, B2O3The loose boron-oxygen triangle formed can absorb free oxygen ions to form a tetrahedral network with a compact structure, thereby improving the devitrification resistance of the glass. At the same time, the free oxygen provided by the alkaline earth metal oxide can reconnect the broken oxygen bridges in the glass network. The short wave transmittance of the glass is related to the breaking degree of the oxygen bridge of the glass, and the shorter the oxygen bridge is broken, the higher the short wave transmittance. Therefore, free oxygen provided by the alkaline earth metal oxide can also play a role in repairing broken oxygen bridges, thereby improving the short-wave transmittance of the glass.
It was experimentally confirmed that too little alkaline earth metal oxide could not provide enough free oxygen ions for the transformation of boron oxygen trigones into a structurally dense tetrahedral network, and thus good devitrification resistance and ideal short-wave transmittance could not be obtained. And excessive alkaline earth metal oxide is added into the glass, because the cation of the alkaline earth metal oxide can also destroy the glass network while providing free oxygen ions, so that the devitrification resistance of the glass is reduced sharply.
Based on the types of alkaline earth metal oxides, BaO has stronger capability of providing free oxygen than SrO, CaO and MgO under the condition of the same content, and is more favorable for improving the devitrification resistance of the glass. At the same time, the density of the glass is higher, which is advantageous for eliminating striae during the forming process. Therefore, in the present invention, BaO is mainly used as the alkaline earth metal oxide, and the content thereof is limited to 6 to 20%, preferably 8 to 18%, and more preferably 8 to 15%.
SrO functions in glass similarly to BaO, but its ability to provide free oxygen is weaker than BaO, and when BaO is replaced in a small amount, the devitrification resistance of glass and the chemical stability of glass can be improved. Since the raw material cost is much higher than that of BaO, the content is limited to 0 to 5%, preferably 0 to 3%, and more preferably not added.
CaO and MgO belong to high-field-strength ions in alkaline earth metal oxides and have a strong aggregation effect on peripheral ions. In the glass of the system, a small amount of CaO and MgO is added to improve the chemical stability of the glass and the glass forming performance of the glass. If the amount is too large, the devitrification resistance of the glass is lowered and the refractive index does not meet the design expectation. Therefore, the content of CaO and MgO is limited to 0 to 5%, preferably 0 to 3%, and more preferably not added.
In the present invention, when the total content of BaO, CaO, SrO and MgO is 10 to 16%, the devitrification resistance and transmittance of the glass are the best.
Li2O、K2O、Na2O is an alkali metal oxide, and in general, such oxides are added to the glass to serve, on the one hand, to lower the Tg of the glass and, on the other hand, to provide more free oxygen in the glass composition, thereby increasing the transmittance of the glass. However, the addition of an excessive amount of alkali metal oxide rapidly accelerates the deterioration of devitrification resistance of the glass, and at the same time, the time for the glass to change from a liquid state to a solid state during cooling molding is prolonged, thereby providing conditions for devitrification and being disadvantageous in large-diameter molding. In addition, when three alkali metal oxides coexist in the glass, the glass can play a role of mutual restriction in the glass crystallization process, and the crystallization resistance is better than that of singly using one alkali metal oxide or two alkali metal oxides. Tests confirm that the Tg temperature of the glass can meet the design requirements and simultaneously has the crystallization resistance and the optimal transmittance when each alkali metal oxide is in the content range described below.
At the same content, Li2O has the strongest ability to lower the Tg of the glass among these three oxides, but if too much Li is added to the glass2O, on one hand, the forming viscosity of the glass is reduced, and the anti-crystallization performance is reduced, and on the other hand, the risk of polluting a mold is easily generated in the precision pressing process of the glass. Therefore, the content thereof is limited to 0 to 2%, preferably 0.2 to 1%, and more preferably 0.2 to 0.8%. Na (Na)2The O content is limited to 0 to 3%, preferably 0.5 to 2%, and more preferably 0.5 to 1.5%. K2The content of O is limited to 0 to 2%, preferably 0.2 to 1%, and more preferably 0.2 to 0.8%.
In the invention, if the total content of the alkali metal oxide exceeds 6 percent, the crystallization resistance is seriously deteriorated, and meanwhile, the material property is lengthened, which is not beneficial to the production of large-caliber thick products; if the total content is less than 1.5%, the Tg temperature does not meet the design requirements. Thus, Li2O、K2O、Na2The total content of O is controlled in the range of 1.5-6%.
La2O3The high-refractivity low-dispersion oxide is a main component for realizing high refractivity and is also a main factor for easy crystallization of glass. In the bulk glass, La2O3If the content of (b) is less than 20%, the designed refractive index cannot be achieved; if the content exceeds 45%, the devitrification resistance of the glass is deteriorated and the material property thereof is also increased. Thus, La2O3The content of (B) is 20 to 45%, preferably 22 to 40%, and more preferably 26 to 38%.
Nb2O5The glass belongs to high-refraction high-dispersion oxide, and the addition of the glass component can improve the refractive index of the glass and adjust the Abbe number of the glass. Nb2O5And La2O3When used together, the anti-devitrification performance of the glass can be improved. In the glass of this system, if the content is less than 5%, the refractive index and Abbe number of the glass do not satisfy the design requirements. If the content is more than 15%, the devitrification resistance of the glass is drastically reduced. Thus, Nb2O5The content of (B) is 5 to 15%, preferably 6 to 14%, and more preferably 7 to 13%.
The inventors have found through their studies that generally, the simpler the composition of the glass system, the greater the probability that the components of the compound will collide with each other and arrange into a certain lattice when the melt is cooled to the liquidus temperature, and the easier the glass will devitrify. In the prior art, Ta is generally used2O5And/or Gd2O3To improve the devitrification resistance of the glass. This, on the one hand, increases the dissolution temperature of the glass, resulting in a decrease in the glass transmittance and even in the generation of platinum inclusions in the glass. On the other hand, Ta is used2O5And/or Gd2O3This leads to an increase in glass cost. Therefore, in the main body glass, Ta which is expensive is not used2O5、Gd2O3To improve the devitrification resistance of the glass, lower cost Y is used2O3、ZrO2、TiO2、WO3The components are combined and reasonably proportioned, and the anti-crystallization performance and the glass stability can be greatly improved by utilizing the synergistic relationship. Meanwhile, the refractive index and the Abbe number of the glass are adjusted, and the cost of the glass is reduced.
Y2O3The glass is high-refraction low-dispersion oxide, if the content is lower than 2%, the anti-crystallization performance is not obviously improved, and if the content exceeds 10%, the anti-crystallization performance of the glass is reduced. Therefore, the content thereof is limited to 2 to 10%, preferably 3 to 9%, and more preferably 4 to 8%.
ZrO2The glass belongs to high-refraction oxide, and the addition of the glass can obviously improve the refractive index of the glass and simultaneously improve the crystallization resistance and the chemical stability of the glass. However, ZrO2The glass belongs to insoluble oxides, and the melting temperature of the glass can be obviously improved when the adding amount is too large, so that the transmittance of the glass can be reduced, and the risks of calculus and crystallization are brought. Therefore, the content thereof is limited to 2 to 7%, preferably 3 to 6%, and more preferably 3.5 to 6%.
TiO2The glass belongs to high-refraction oxide, and the addition of the glass can obviously improve the refractive index and dispersion of the glass and simultaneously improve the devitrification resistance of the glass. If the content is less than 1%, the refractive index and dispersion can not meet the design requirements, and simultaneouslyThe high resistance to devitrification is not significant. However, too much TiO2The addition of glass impairs the transmittance of the glass and reduces the devitrification resistance of the glass. Thus, TiO2The content of (B) is limited to 1 to 6.5%, preferably 2 to 6%, and more preferably 3 to 6%.
Further, Ti ions are present in such glasses [ TiO4]And [ TiO ]6]Two different coordination structures, Ti ion with [ TiO ] under the condition of sufficient free oxygen of glass system4]The coordination structure enters the glass network, so that the network structure of the glass and the devitrification resistance of the glass can be enhanced. More importantly, in the high-refractive-index lanthanide glass containing Ti, the coordination structure of Ti in the glass has great influence on the short-wave transmittance. When Ti ion is [ TiO ]4]When the coordination structure of the titanium dioxide enters the glass network, Ti ions are not easily influenced by atmosphere and smelting temperature, the short wave transmittance of the glass is increased, the density of the glass network is increased, and the anti-crystallization capacity is enhanced. If Ti ion is [ TiO ]6]The coordination structure enters the glass network and exists as a network external body, the electronic outer layer structure of the coordination structure is easily influenced by the polarization of surrounding ions and the melting temperature and atmosphere, and the short-wave transmittance of the glass is rapidly reduced. Therefore, in the design of glass components, the reasonable proportion of each component is considered to ensure that TiO is used2Composition formation [ TiO ] as far as possible4]The coordination structure, thereby improving the short wave transmittance and the anti-crystallization performance of the glass. The inventors have intensively studied and found that the coordination structure of Ti ions is related to the amount of free oxygen in the glass system. In the present glass system, the B ion and the Ti ion have the ability to obtain free oxygen in the glass system, and the alkali metal and the alkaline earth metal are main supply sources of the free oxygen. When B ions and Ti ions exist in a glass system at the same time, the binding capacity of the B ions and free oxygen is far greater than that of the Ti ions, so that the free oxygen in the system can be preferentially bound with the B ions, and after reaction equilibrium is reached, the residual free oxygen can be bound with the Ti ions to form [ TiO ]4]The coordination structure enters the glass network. At the same time, the ability of the B ions to bind free oxygen also correlates with SiO in the glass2In relation to the content, one [ BO4]The structure needs oneThe silicon-oxygen tetrahedron isolates the charge. When there is no silicon-oxygen tetrahedron isolation in the system, the B ion will not form [ BO ] in combination with free oxygen4]A tetrahedron. Therefore, the coordination structure of Ti ions in glass is mainly related to silicon oxide, boron oxide, alkali metal oxide and alkaline earth metal oxide. In other words, TiO in the glass2The influence of the content of (A) on the short-wave transmittance is mainly in close synergistic relationship with the content of the oxides.
The inventor researches and discovers that (Li)2O+Na2O+K2O+BaO+SrO+CaO+MgO-SiO2)/TiO2When the value of (A) is more than 1, the glass has a high short-wave transmittance.
WO3Also belongs to the high-refractivity and high-dispersion oxide which is easy to crystallize, and can play the roles of adjusting the refractivity and the dispersion and improving the crystallization resistance of the glass when being added into the glass. In addition, WO3TiO reduction by addition to glass systems2The amount of (3) is so large that the short-wave transmittance of the glass can be improved. If the content is less than 1%, the improvement of the anti-crystallization performance and the transmittance are not obvious. If the content is more than 5%, the devitrification resistance of the glass is lowered, and at the same time, the cost of the glass is increased and the transmittance is lowered. Therefore, the content thereof is limited to 1 to 5%, preferably 1 to 4%, and more preferably 2 to 4%.
Further, the above six oxides satisfy the above-specified composition range while satisfying (La) at the same time2O3+Nb2O5)/(TiO2+Y2O3+WO3+ZrO2) When the ratio of (A) to (B) is greater than 1, the glass has the best devitrification resistance.
Sb2O3Is a fining agent, and is added into the glass to facilitate bubble elimination. In the present invention, the content is limited to 0 to 1%, preferably 0 to 0.5%, and more preferably not added.
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 transmittance at a wavelength of 400nm was measured according to the method specified in GB/T7962.12-2010.
The Tg temperature of the glass was measured according to the method specified in GB/T7962.16-2010.
The devitrification resistance of the glass during the press forming process was tested using the following method:
processing an experimental sample into a specification of 20 × 10mm, polishing two surfaces, putting the sample into a crystallization furnace with the temperature of Tg +200 ℃ for heat preservation for 30 minutes, taking out and cooling, polishing two large surfaces, and judging the crystallization performance of the glass according to the following table 1, wherein the A grade is the best, and the E grade is the worst.
Table 1: classification and judgment criteria for devitrification
| Numbering | Rank of | Standard of merit |
| 1 | A | Devitrified particles without macroscopic view |
| 2 | B | The crystallized particles are visible to the naked eye, and are small in number and dispersed |
| 3 | C | Larger dispersed or denser, smaller devitrified particles are visible to the naked eye |
| 4 | D | The crystallized grains are larger and dense |
| 5 | E | Complete devitrification and devitrification of glass |
The anti-devitrification capability of the glass in the cooling and pouring stage is tested whether the glass has the large-caliber forming performance by using the following experimental method:
all experimental samples were dosed in 0.8L volumes and a platinum crucible of 1L volume was used to melt the raw material. After the clarification and homogenization of the glass are finished, the temperature of the molten glass is reduced to 1150 ℃, and the molten glass is poured into a cast iron mold with the length of 170mm, the width of 150mm and the depth of 75mm (the mold is insulated at 550 ℃ before pouring), as shown in figure 1-2, wherein the mold comprises a bottom mold 1, a side plate 2, a bottom plate 3 and a support 4, and the support 4 is made of heat-resistant cast iron. And (4) placing the cooled glass into a muffle furnace for annealing. And taking out the glass after annealing, observing whether devitrification is generated in the glass block, and if not, proving that the glass has good devitrification resistance when being cooled and has the capability of thick-specification large-caliber forming.
Through tests, the optical glass of the invention has the following properties: the refractive index is between 1.81 and 1.87, and the Abbe number is between 32 and 38; an internal transmittance (tau 400nm) at a wavelength of 400nm of more than 87%; tg temperature lower than 630 ℃; the devitrification resistance of the glass is A grade; under the pouring conditions and cooling conditions specified above, no devitrification occurs inside the glass.
Examples
In order to further understand the technical solution of the present invention, examples of the optical glass of the present invention will now be described, and 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 2 to 3 were prepared by weighing and mixing the ordinary raw materials (such as oxides, hydroxides, carbonates, nitrates, etc.) for optical glasses in the ratios of the respective examples shown in tables 2 to 3, placing the mixed raw materials in a platinum crucible, melting at 1260-.
Tables 2 to 3 show compositions, refractive indices (nd), Abbe numbers (vd), internal transmittances at 400nm wavelength (. tau.400 nm), Tg temperatures, and Li values of examples 1 to 20 of the present invention2O+K2O+Na2The total O content is represented by K1, and the total BaO + CaO + SrO + MgO content is represented by K2, (Li)2O+Na2O+K2O+BaO+SrO+CaO+MgO-SiO2)/TiO2Is represented by K3 (La)2O3+Nb2O5)/(TiO2+Y2O3+WO3+ZrO2) The value of (A) is represented by K4, the devitrification resistance rating of the glass is represented by A, and the devitrification inside the glass under the above-specified casting conditions is represented by B.
TABLE 2
TABLE 3
Claims (10)
1. The lanthanum flint optical glass is characterized by comprising the following components in percentage by weight: SiO 22 2-10％、B2O3 12-25％、TiO2 1-6.5％、La2O3 20-45％、Y2O3 2-10％、ZrO2 2-7％、Nb2O5 5-15％、WO31 to 5 percent of BaO, 10.10 to 15 percent of BaO and no ZnO.
2. The lanthanum flint optical glass of claim 1, further comprising: CaO 0-5%, SrO 0-5%, MgO 0-5%, Li2O 0-2％、K2O 0-2％、Na2O 0-3％、Sb2O3 0-1％。
3. The lanthanum flint optical glass of claim 2, wherein Li is2O+K2O+Na2The total content of O is 1.5-6%.
4. The lanthanum flint optical glass of claim 1, wherein SiO23-8% and/or B2O314-23% and/or TiO22-6% and/or La2O322-40% and/or Y2O33-9% and/or ZrO23-6% and/or Nb2O56-14% and/or WO31-4% and/or CaO 0-3% and/or SrO 0-3% and/or MgO 0-3% and/or Li200.2-1% and/or K2O0.2-1% and/or Na20.5-2% of O and/or Sb2O3 0-0.5％。
5. The lanthanum flint optical glass of claim 1, wherein SiO23.5-6.5% and/or B2O316-22% and/or TiO23-6% and/or La2O326-38% and/or Y2O34-8% and/or ZrO23.5-6% and/or Nb2O57-13% and/or WO32-4% and/or Li2O0.2-0.8% and/or K2O0.2-0.8% and/or Na2O 0.5-1.5％。
6. The lanthanum flint optical glass of claim 1, wherein the total content of BaO + CaO + SrO + MgO is 10.10-16%.
7. The lanthanum flint optical glass of claim 1, wherein (Li)2O+Na2O+K2O+BaO+SrO+CaO+MgO-SiO2)/TiO2Is greater than 1.
8. The lanthanum flint optical glass of claim 1, wherein (La)2O3+Nb2O5)/(TiO2+Y2O3+WO3+ZrO2) Is greater than 1.
9. The lanthanum flint optical glass of claim 1, wherein the glass has a refractive index of 1.81 to 1.87 and an abbe number of 32 to 38.
10. The lanthanum flint optical glass of claim 1, wherein the glass has a Tg of less than 630 ℃, a τ 400nm of greater than 87%, and a devitrification resistance of class a.
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| JP7224099B2 (en) * | 2016-10-03 | 2023-02-17 | 株式会社オハラ | Optical glass, preforms and optical elements |
| CN106830670B (en) * | 2016-12-30 | 2019-05-31 | 中国科学院西安光学精密机械研究所 | Lanthanum crown LaK3 series space radiation resistance optical glass and preparation method thereof |
| CN106830672B (en) * | 2016-12-30 | 2019-05-31 | 中国科学院西安光学精密机械研究所 | Lanthanum flint LaF3 series space radiation resistance optical glass and preparation method thereof |
| CN106927676B (en) * | 2017-02-22 | 2019-03-08 | 中国科学院上海光学精密机械研究所 | The flint optical glass with heavy lanthanum of high-refractivity and low-dispersion |
| CN112424134B (en) * | 2018-07-18 | 2023-04-18 | 株式会社小原 | Optical glass and optical element |
| CN111217522A (en) * | 2018-11-27 | 2020-06-02 | 宜城市泳瑞玻璃科技有限公司 | Optical glass suitable for secondary compression and aspheric surface precision compression |
| 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 |
| JP7433764B2 (en) * | 2019-01-18 | 2024-02-20 | Hoya株式会社 | Method for promoting improvement of transmittance of glass, method for manufacturing glass, and glass |
| CN110590154A (en) * | 2019-10-11 | 2019-12-20 | 成都光明光电股份有限公司 | Optical glass |
| CN111977970B (en) * | 2020-09-07 | 2022-04-15 | 成都光明光电股份有限公司 | Optical glass and optical element |
| CN113816600A (en) * | 2021-08-31 | 2021-12-21 | 甘肃光轩高端装备产业有限公司 | Glass composition, lanthanide glass, preparation method and application of lanthanide glass, and lanthanide glass wafer |
| CN115028354B (en) * | 2022-06-22 | 2023-09-05 | 成都光明光电股份有限公司 | Optical glass and optical element |
| CN116750966A (en) * | 2023-06-20 | 2023-09-15 | 成都光明光电有限责任公司 | Radiation-resistant glass |
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| JP6434078B2 (en) | 2018-12-05 |
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| TWI646064B (en) | 2019-01-01 |
| CN110342815A (en) | 2019-10-18 |
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| JP2019059667A (en) | 2019-04-18 |
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