CN116239299A - Optical glass and preparation method and application thereof - Google Patents
Optical glass and preparation method and application thereof Download PDFInfo
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- CN116239299A CN116239299A CN202211715917.0A CN202211715917A CN116239299A CN 116239299 A CN116239299 A CN 116239299A CN 202211715917 A CN202211715917 A CN 202211715917A CN 116239299 A CN116239299 A CN 116239299A
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention provides optical glass and a preparation method and application thereof. The optical glass composition comprises the following components in percentage by mass: 3 to 50.0 percent of SiO 2 0.01 to 15.0 percent of Li 2 O+Na 2 O+K 2 O, baO 6.0-35 wt%, B0.01-15.0 wt% 2 O 3 10% -45% of Nb 2 O 5 ZrO 0.01% -15% 2 TiO 8.5-35.0% 2 5 to 55 percent of La 2 O 3 Bi of 0.01-10.0% 2 O 3 +Gd 2 O 3 +Y 2 O 3 0 to 2.0 percent of CaO,0 to 3.0 percent of SrO and 0 to 10.0 percent of ZnO. The optical glass provided by the invention has a lower expansion coefficient and a lower density, and accords with the development trend of light weight of optical devices. Meanwhile, the glass prepared by the preparation method provided by the invention is not easy to split phases, high in uniformity and low in processing and molding difficulty, and can reduce the production cost. Therefore, the optical glass provided by the invention has wide applicationThe application prospect is good.
Description
Technical Field
The invention belongs to the field of glass products, and particularly relates to optical glass and a preparation method and application thereof.
Background
In recent years, market trends of both optical technology and optoelectronic technology (application fields of imaging, projection, laser technology and optical communication engineering technology) have been increasingly advanced toward miniaturization, and optical elements applied to optical systems have also been advanced toward miniaturization, weight saving, and high performance. The optical glass with high refractive index and high dispersion can effectively shorten the total optical length of the lens, miniaturize an imaging system, and is beneficial to the development trend of miniaturization of optical devices, because the optical glass with high refractive index has wide application prospect.
The high refractive optical glass is a necessary material for AR glasses, glasses type displays, glasses with projectors, virtual image display devices, and the like. High refractive index optical glasses are currently commercially available that typically employ relatively high levels of rare earth metal oxides to achieve high refractive effects. However, when a high content of rare earth metal oxide is used, the obtained glass generally has a high expansion coefficient and a high density, and is extremely easy to phase-separate and difficult to be homogenized in the forming process, and the color of the glass is yellowish brown, so that the optical performance of the glass is affected.
Therefore, there is a need in the art for an optical glass that satisfies both high refractive index, low density, and uniformity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides optical glass. The optical glass prepared by regulating and controlling the components and the proportion under certain production conditions has the advantages of high refractive index, low density, low expansion coefficient, difficult phase separation, high uniformity and the like. The specific contents are as follows:
in a first aspect, the present invention provides an optical glass comprising, in mass percent based on the total weight of the glass composition: 3 to 50.0 percent of SiO 2 0.01 to 15.0 percent of Li 2 O+Na 2 O+K 2 O, baO 6.0-35 wt%, B0.01-15.0 wt% 2 O 3 10% -45% of Nb 2 O 5 ZrO 0.01% -15% 2 TiO 8.5-35.0% 2 5 to 55 percent of La 2 O 3 Bi of 0.01-10.0% 2 O 3 +Gd 2 O 3 +Y 2 O 3 0 to 2.0 percent of CaO,0 to 3.0 percent of SrO and 0 to 10.0 percent of ZnO.
In some embodiments, the optical glass comprises, in mass percent, based on the total weight of the glass composition: 5 to 47.5 percent of SiO 2 0.01 to 12 percent of Li 2 O+Na 2 O+K 2 10.5 to 30.5 percent of O,1.1 to 12 percent of BaO and B 2 O 3 12.5 to 37.5 percent of Nb 2 O 5 ZrO 1.0% -13.5% 2 12% -30% of TiO 2 10 to 50.4 percent of La 2 O 3 Bi of 0.05-8.5% 2 O 3 +Gd 2 O 3 +Y 2 O 3 0.01 to 1.7 percent of CaO,0.01 to 2.7 percent of SrO and 0 to 10.0 percent of ZnO.
In some embodiments, the mass percentages of the components are calculated by substituting the mass percentages into the formula to obtain Nb 2 O 5 +La 2 O 3 More than or equal to 18.5 percent, and/or ZrO 2 +SiO 2 +B 2 O 3 Not less than 8%, and/or ZrO 2 +TiO 2 +BaO is more than or equal to 30%; preferably, it is: nb (Nb) 2 O 5 +La 2 O 3 Not less than 23.5.5%, and/or ZrO 2 +SiO 2 +B 2 O 3 More than or equal to 10 percent, and/or ZrO 2 +TiO 2 +BaO≥35.5％。
In some embodiments, a fining agent is also included in the glass composition of the optical glass; the clarifier is contained in an amount of 0.01 to 0.5% by mass based on the total weight of the glass composition.
In some embodiments, the clarifying agent is at least one of chloride, fluoride, and sulfide, preferably chloride.
In some embodiments, the optical glass has a refractive index greater than 1.9, and/or a visible light transmittance greater than 85%, and/or a density of 4g/cm or less 3 。
For example, the optical glass may have a refractive index of 1.92, 1.93, 1.95, 1..96, 1.97, 1.98, 2.08, or 2.12, a visible light transmittance of 85%, 86%, 87%, 88%, 89%, or 90%, and a density of 4g/cm 3 、3.91g/cm 3 、3.89g/cm 3 、3.87g/cm 3 、3.64g/cm 3 、3.61g/cm 3 、3.58g/cm 3 、3.52g/cm 3 Or 3.46g/cm 3 。
In some embodiments, the optical glass has a glass liquidus temperature TL of less than 1150 ℃ and/or a glass transition temperature Tg of less than or equal to 620 ℃.
For example, the glass liquidus temperature TL is 1143 ℃, 1135 ℃, 1121 ℃, 1106 ℃, 1097 ℃, or 1085 ℃, and the glass transition temperature Tg may be 620 ℃, 619 ℃, 616 ℃, 615 ℃, 613 ℃, 614 ℃, 609 ℃, 608 ℃.
In a second aspect, the present invention provides a method for producing the optical glass described in the first aspect. The method comprises the following steps:
fully stirring and mixing the raw materials according to the formula proportion to obtain a batch mixture;
melting the batch mixture at a high temperature;
casting the melted mixture into a mould, and annealing to obtain a glass raw sheet;
and processing the glass raw sheet to obtain a glass product.
In some embodiments, the temperature of melting is 1200 to 1500 ℃ for 3 to 8 hours; the annealing temperature is 550-630 ℃ and the annealing time is 1-3 h.
For example, the melting temperature may be in the range of 1200 ℃,1250 ℃,1300 ℃,1350 ℃,1400 ℃, 1450 ℃,1500 ℃, and any combination thereof, and the time may be in the range of 3h,5h,6h,7h,8h, and any combination thereof; the temperature of the annealing may be 550 ℃,570 ℃,580 ℃,590 ℃,600 ℃,620 ℃,630 ℃, and any combination thereof; the time may be in the range of 1h,1.5h,2h,2.5h,3h, and any combination thereof.
In a third aspect, the present invention provides an optical glass according to the first aspect.
The invention provides optical glass and a preparation method and application thereof. The optical glass composition comprises the following components in percentage by mass: 3 to 50.0 percent of SiO 2 0.01 to 15.0 percent of Li 2 O+Na 2 O+K 2 O, baO 6.0-35 wt%, B0.01-15.0 wt% 2 O 3 10% -45% of Nb 2 O 5 ZrO 0.01% -15% 2 TiO 8.5-35.0% 2 5 to 55 percent of La 2 O 3 Bi of 0.01-10.0% 2 O 3 +Gd 2 O 3 +Y 2 O 3 . The optical glass provided by the invention has higher refractive index and smaller density, and accords with the development trend of light weight of optical devices. Meanwhile, the glass prepared by the preparation method provided by the invention is not easy to split, high in uniformity and low in processing and forming difficulty, and can reduce the production cost. Therefore, the optical glass provided by the invention has wide application prospect.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof. The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The embodiment of the invention provides optical glass. The specific contents are as follows: :
in a first aspect, embodiments of the present invention provideAn optical glass is provided, the components of the optical glass composition comprising, in mass percent, based on the total weight of the glass composition: 3 to 50.0 percent of SiO 2 0.01 to 15.0 percent of Li 2 O+Na 2 O+K 2 O, baO 6.0-35 wt%, B0.01-15.0 wt% 2 O 3 10% -45% of Nb 2 O 5 ZrO 0.01% -15% 2 TiO 8.5-35.0% 2 5 to 55 percent of La 2 O 3 Bi of 0.01-10.0% 2 O 3 +Gd 2 O 3 +Y 2 O 3 。
In the present embodiment, siO 2 Is a main network forming body of glass and is a component for improving the stability and chemical durability of the glass. SiO (SiO) 2 The content ratio of (2) is 3-50%. SiO (SiO) 2 When the content ratio is 50% or less, a component for obtaining a higher refractive index may be contained. SiO for ensuring glass stability 2 The content of (2) is preferably 3% or more, more preferably 5% or more, and SiO 2 The content ratio of (2) is preferably 50% or less, more preferably 47.5% or less.
In the present embodiment, li 2 O、Na 2 O、K 2 O is the network exo-oxide of the glass structure. The glass flux has the characteristics of reducing the high-temperature viscosity of the glass and improving the melting performance of the glass, is a good glass flux, and can reduce the glass transition temperature. However, if the alkali metal content is too large, the viscosity curve becomes steep, which is unfavorable for glass production, and therefore, li 2 O+Na 2 O+K 2 The content of O is 15.0% or less, and more preferably, the content of alkali metal is 0.01% to 12%.
In this embodiment, baO mainly increases the refractive index, and too low an effect of increasing the refractive index cannot be obtained, but when the amount of BaO is large, the density tends to be large. The BaO content is set to 6-35%, and the BaO content is preferably set to 10.5-30.5%.
In the present embodiment, B 2 O 3 Can be used as matrix for forming network structure, and can be independently formed into glass, and its addition can raise toughness of glass, at the same time B 2 O 3 Also good flux, can greatly reduce glass melting temperature, is beneficial to the vitrification process, but too much content is detrimental to the thermal stability and refractive index improvement, therefore, B, as described above 2 O 3 The content ratio of (B) in the composition is 0.01-15.0% 2 O 3 The content of (2) is preferably 1.1% to 12%.
In the present embodiment, nb 2 O 5 The glass has a high refractive index and a small Abbe number, and is too low to satisfy the purpose of increasing the refractive index, but when the content is too high, deterioration of the internal transmittance can be caused. Thus, as described above, nb in the composition 2 O 5 The content of (2) is preferably 10% to 45%, more preferably 12.5% to 37.5%.
In the present embodiment, zrO 2 Is a component for improving the refractive index of glass and improving the chemical durability of glass. By containing ZrO 2 The mechanical properties of the glass can be improved. On the other hand, if ZrO 2 Too much, devitrification becomes easy. Thus, zrO 2 The content ratio of (2) is preferably 0.01% to 15.0%, more preferably 1.0% to 13.5%.
In the present embodiment, tiO 2 The main effect is to increase the refractive index of the glass, increase the dispersed components of the glass, on the other hand, if TiO 2 Too much tends to color, resulting in a decrease in transmittance, and too low to achieve the purpose of increasing refractive index, so TiO 2 The content ratio of (2) is preferably 8..5% to 35%, more preferably 12% to 30%.
In the present example, la 2 O 3 Is a component for increasing the refractive index of the glass, and if the refractive index is too low, a combination of a high refractive index and a high Abbe number cannot be achieved, but if La 2 O 3 Too large an amount increases the viscosity of the glass too much and increases the tendency for devitrification to occur. Therefore La 2 O 3 The content ratio of (2) is preferably 5% to 55%, more preferably 10% to 50.4%.
In the present embodiment, gd 2 O 3 Having the effect of increasing refractive index without decreasing Abbe numberAs a result, the component is an expensive glass component and too much Gd-containing 2 O 3 Reduce the internal transmittance, bi 2 O 3 Has the effect of significantly increasing the refractive index due to Bi 2 O 3 The intrinsic color of (C) has an adverse effect on the transmittance of the glass, so that too high is not desirable to cause the blackening of the glass color to result in a decrease in transmittance, and too low is not desirable to achieve the purpose of increasing the refractive index, Y 2 O 3 Has the effects of improving refractive index and reducing high-temperature viscosity due to Y 2 O 3 Too high may cause glass to be easily devitrified while increasing costs, and thus is not preferable. Too low a content to achieve the object of increasing the refractive index, bi 2 O 3 +Gd 2 O 3 +Y 2 O 3 The content of (2) is preferably 0.01% to 10%, more preferably 0.05% to 8.5%.
In some embodiments, the optical glass has a refractive index greater than 1.9, and/or a visible light transmittance greater than 85%, and/or a density of 4g/cm or less 3 。
For example, the optical glass may have a refractive index of 1.92, 1.93, 1.95, 1..96, 1.97, 1.98, 2.08, or 2.12, a visible light transmittance of 85%, 86%, 87%, 88%, 89%, or 90%, and a density of 4g/cm 3 、3.91g/cm 3 、3.89g/cm 3 、3.87g/cm 3 、3.64g/cm 3 、3.61g/cm 3 、3.58g/cm 3 、3.52g/cm 3 Or 3.46g/cm 3 。
The optical glass provided by the embodiment of the invention adopts SiO 2 、BaO、B 2 O 3 、Nb 2 O 5 、ZrO 2 、TiO 2 、Bi 2 O 3 Gd (Gd) 2 O 3 The function of rare earth metal is coordinated, so as to achieve the purpose of high refractive index. And the contents of the oxides are uniformly regulated, so that the glass has the characteristics of high refractive index and low density, and the light weight of one of the development trends of the current optical devices is met, and the burden of a wearer is reduced.
In some embodiments, the optical glass has a glass liquidus temperature TL of less than 1150 ℃ and/or a glass transition temperature Tg of less than or equal to 620 ℃.
For example, the glass liquidus temperature TL is 1143 ℃, 1135 ℃, 1121 ℃, 1106 ℃, 1097 ℃, or 1085 ℃, and the glass transition temperature Tg may be 620 ℃, 619 ℃, 616 ℃, 615 ℃, 613 ℃, 614 ℃, 609 ℃, 608 ℃.
The glass liquidus temperature TL of the optical glass provided by the embodiment of the invention is less than 1150 ℃, and the processing and forming difficulty of the glass with low liquidus temperature is correspondingly low, and the glass is not easy to devitrify. Therefore, the optical glass provided by the embodiment of the invention also has the advantage of low processing and forming difficulty. Meanwhile, the optical glass provided by the embodiment of the invention has low phase separation trend and high uniformity.
In some embodiments, the mass percentages of the components are calculated by substituting the mass percentages into the formula to obtain Nb 2 O 5 +La 2 O 3 ≥18.5％；ZrO 2 +SiO 2 +B 2 O 3 ≥8％；ZrO 2 +TiO 2 +BaO≥30％。
In the embodiment, zrO is set in the embodiment so as to ensure that the glass forming ability of the material is also high 2 +SiO 2 +B 2 O 3 Not less than 8%, the mechanical property of the glass can be improved, and the devitrification risk of the glass is reduced; on the other hand, nb 2 O 5 +La 2 O 3 ≥18.5％，ZrO 2 +TiO 2 +BaO is more than or equal to 30 percent, and the refractive index of the glass can be improved.
In some embodiments, preferably, the mass percentages of the components are calculated by substituting the mass percentages into the formula to obtain Nb 2 O 5 +La 2 O 3 ≥23.5％；ZrO 2 +SiO 2 +B 2 O 3 ≥10％；ZrO 2 +TiO 2 +BaO≥35.5％。
In some embodiments, the optical glass composition further comprises, in mass percent: 0 to 2.0 percent of CaO.
In this example, caO is a glass structure network exo-oxide. CaO is a component that significantly improves the meltability by lowering the high-temperature viscosity without lowering the strain point. Of alkaline earth metals, caO is an effective component for increasing Young's modulus of glass without increasing density of glass, and has a thermal expansion coefficient, and the content ratio of CaO is 0 to 2.0%. If the content is too low, the effect is not remarkable, and if the content is too high, the glass tends to be devitrified easily, and the thermal expansion coefficient is greatly increased, so that the content is preferably 0.01 to 1.7%.
In some embodiments, the optical glass composition further comprises, in mass percent: 0% -3.0% of SrO.
In this example, srO is a component that improves the meltability of glass, suppresses devitrification, and adjusts the optical constant of glass. On the other hand, when the amount of SrO is too large, devitrification is promoted. The content ratio of SrO is set to 0 to 3.0%, and thus the content ratio of SrO is preferably 0.01 to 2.7%.
In some embodiments, the optical glass composition further comprises, in mass percent: 0% -10.0% of ZnO.
In this example, znO can improve the mechanical properties of the glass, increase the young's modulus of the glass, and have less impact on the density and coefficient of thermal expansion of the glass. At the same time zinc oxide can be combined with high refractive index oxide (ZrO 2 、TiO 2 、La 2 O 3 Etc.) to stabilize the glass structure. When the amount is too large, the glass tends to be crystallized, so that the ZnO content is preferably 0 to 10%.
In some embodiments, a fining agent is also included in the glass composition of the optical glass; the content of the clarifying agent is 0.01-0.5% by mass based on the total weight of the glass composition.
In this example, the glass composition of the present invention further comprises a fining agent in an amount of 0.01 to 0.5% by mass based on the total weight of the glass composition. In particular, the clarifying agent is at least one selected from the group consisting of chlorides, fluorides and sulfides, preferably chlorides, such as NaCl, NH 4 Cl, and the like.
In some embodiments, the glass composition of the optical glass is free of As 2 O 3 And Sb (Sb) 2 O 3 。
Due to As 2 O 3 And Sb (Sb) 2 O 3 Toxic, in order to avoid harm to human body, the glass composition of the present example does not contain As 2 O 3 And Sb (Sb) 2 O 3 。
In a second aspect, the present invention provides a method for producing the optical glass described in the first aspect. The method comprises the following steps:
according to the formula proportion of the first aspect, fully stirring and mixing the raw materials to obtain a batch mixture;
melting the batch mixture at a high temperature;
casting the melted mixture into a mould, and annealing to obtain a glass raw sheet;
and processing the glass raw sheet to obtain a glass product.
In this example, the melting may be performed in a platinum-rhodium crucible at a treatment temperature of 1200 to 1500 ℃ for 3 to 8 hours. For example, the melting temperature may be in the range of 1200 ℃,1250 ℃,1300 ℃,1350 ℃,1400 ℃, 1450 ℃,1500 ℃, and any combination thereof, and the time may be in the range of 3h,5h,6h,7h,8h, and any combination thereof. The specific melting temperature and melting time can be determined by those skilled in the art according to the actual situation, and are well known to those skilled in the art and will not be described here again.
According to the method of the invention, stirring and mixing are conventional homogenization methods in the field, for example, the bubbles in the molten glass can be escaped through stirring and the components in the molten glass are uniformly distributed.
According to the method of the present invention, the casting is performed in a conventional casting molding manner in the art, for example, it may be performed in a stainless steel mold, and specific steps and condition parameters are well known in the art and will not be described herein.
In this example, the annealing temperature is 550-630℃and the time is 1-3 hours. For example, the temperature of the anneal may be in the range of 550 ℃,570 ℃,580 ℃,590 ℃,600 ℃,620 ℃,630 ℃, and any combination thereof; the time may be in the range of 1h,1.5h,2h,2.5h,3h, and any combination thereof. The specific annealing temperature and annealing time can be determined by those skilled in the art according to the actual situation, and are well known to those skilled in the art, and will not be described herein.
In this example, the processing is not particularly limited, and various mechanical processing methods common in the art may be used, for example, slicing, grinding, polishing, and the like may be performed on the product obtained by the annealing treatment, and chemical tempering may be performed as needed.
In this embodiment, the chemical strengthening treatment includes one chemical strengthening treatment and/or a plurality of chemical strengthening treatments. The chemical strengthening is realized by ion exchange on the surface of the glass plate, the chemical strengthening liquid is sodium nitrate, potassium nitrate and/or mixed melt of the sodium nitrate and the potassium nitrate, the ion exchange temperature is 390-450 ℃, the specific strengthening temperature and molten salt proportion can be determined by a person skilled in the art according to actual conditions, and the specific strengthening temperature and molten salt proportion are well known to the person skilled in the art and are not repeated herein.
The glass prepared by the preparation method has the refractive index of more than 1.9, the visible light transmittance of more than 85 percent and the density of less than or equal to 4g/cm 3 . The glass composition and the optical glass prepared by the preparation method provided by the invention have the advantages of lower expansion coefficient and lower density, and accord with the development trend of light weight of optical devices. Meanwhile, the glass prepared by the preparation method provided by the invention is not easy to split phases, high in uniformity and low in processing and forming difficulty, and can reduce the production cost.
In a third aspect, the present invention provides an optical glass according to the first aspect. Specifically, the present invention can be applied to various scenes requiring optical glass, such as AR glasses, glasses type displays, glasses with projectors, and virtual image display devices.
In order to make the technical concept of the present invention more clearly understood by those skilled in the art, the present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples only. Meanwhile, in the following examples, each material used was commercially available as not specifically described, and the method used was a conventional method in the art as not specifically described. The specific contents are as follows:
in the following examples and comparative examples, glass density in g/cm was measured with reference to ASTM C-693 3 。
The coefficient of thermal expansion of glass at 50-350℃was measured with a horizontal dilatometer in units of 10 with reference to ASTM E-228 -7 /℃。
Young's modulus of glass in GPa was measured by reference to ASTM C-623 using a materials mechanics tester.
The transmittance of the glass corresponding to a wavelength of 550nm was measured by using a UV-2600 ultraviolet-visible spectrophotometer.
The glass refractive index was measured using a WYV-S digital V prism refractometer.
Tg was measured using a horizontal dilatometer in degrees Celsius.
The glass height Wen Nianwen curve is determined with reference to ASTM C-965 using a rotary high temperature viscometer, wherein 200P corresponds to the melting temperature Tm in degrees Celsius.
The glass liquidus temperature TL was measured in degrees Celsius using a step furnace method with reference to ASTM C-829.
Examples 1-12 and comparative examples 1-4 were conducted as follows to prepare corresponding glass products.
The components were weighed according to the glass compositions shown in tables 1, 2 and 3, mixed well, poured into a platinum crucible, heated in a high temperature furnace at 1400 ℃ for 5 hours, and stirred using a platinum rod to discharge bubbles. Pouring the melted glass liquid into a stainless steel cast iron grinding tool, forming a specified blocky glass product, then preserving the glass product in an annealing furnace for 2 hours at 600 ℃, then reducing the temperature to 300 ℃ at 1 ℃ per minute, and turning off a power supply and cooling to room temperature along with the furnace. Cutting, grinding and polishing the glass product, and then cleaning with deionized water and drying to obtain a glass finished product. The respective properties of the respective glass products were measured, and the results are shown in tables 1, 2 and 3.
TABLE 1 measurement of various properties of the glass products obtained in examples 1-6
TABLE 2 measurement of various Properties of the finished glass products obtained in examples 7 to 12
TABLE 3 measurement of various properties of the glass products obtained in comparative examples 1 to 4
Note that: in tables 1 to 3 above, "-" means: the method is free; "/" means: and no.
From the performance test results of tables 1-3 above, it can be seen that:
1. the optical glass provided in this embodiment adopts SiO2, baO, B2O3, nb2O5, zrO2, tiO2, bi2O3, and Gd2O3 to perform functional coordination on rare earth metals, and the refractive index may be up to 2.08 (as shown in the performance test results of embodiment 1).
2. The optical glass provided in this example can have a lower density by uniformly adjusting the component content, and its refractive index is as high as 1.96 (as shown in the performance test results of example 6). That is, the optical glass provided in the present embodiment satisfies the light weight requirement required at present, and can reduce the burden on the wearer.
3. The optical glasses provided in this example all have lower liquidus temperatures TL, as low as 1085 ℃ (as shown in the performance test results of example 1), while the highest liquidus temperature TL is also lower than 1150 ℃ (as shown in the performance test results of example 3), and the processing difficulty of the glass with low liquidus temperature is correspondingly lower, and the glass is not easy to devitrify. Therefore, the optical glass provided by the embodiment of the invention also has the advantage of low processing and forming difficulty.
4. The optical glasses provided in this example all had lower glass transition temperatures Tg, as low as 608 ℃ (as shown in the performance test results of example 4), while the highest glass transition temperature Tg was also only 620 ℃ (as shown in the performance test results of example 3). The glass transition temperature (Tg) is the lowest temperature at which a molecular chain segment can move, and the height of the Tg is directly related to the flexibility of the molecular chain, and the larger the flexibility of the molecular chain is, the lower the glass transition temperature is. Therefore, the optical glass provided by the embodiment of the invention also has the characteristic of higher flexibility of a molecular chain, thereby further reducing the difficulty of processing and forming.
5. As shown by the performance test results of examples 1-12, when Nb 2 O 5 +La 2 O 3 ≥18.5％，ZrO 2 +SiO 2 +B 2 O 3 ≥8％，ZrO 2 +TiO 2 When +BaO is more than or equal to 30%, the prepared optical glass has the advantages of high refractive index, low density, low TL and Tg, low phase separation trend, high uniformity and the like. As is clear from comparative examples 1 to 3, when Nb 2 O 5 +La 2 O 3 ≥18.5％，ZrO 2 +SiO 2 +B 2 O 3 ≥8％，ZrO 2 +TiO 2 When any one of +BaO is more than or equal to 30 percent and meets the requirement, the prepared optical glass cannot have the advantages of high refractive index, low density, low TL and Tg, low phase separation trend, high uniformity and the like. That is, the optical glass prepared according to the component requirements provided in this example can meet the current industry requirements.
6. As shown by the performance test results of example 1 and comparative example 4, when water quenching was not used during the preparation, the obtained optical glass had poor performance. From this, it can be seen that the optical glass component provided in this embodiment, after being prepared by the method provided in this embodiment, has the advantages of high refractive index, low density, low TL and Tg, low phase separation tendency, high uniformity, and the like.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.
The above has described an optical glass, its preparation method and application provided by the invention in detail, the specific examples have been used herein to illustrate the principle and implementation of the invention, the above examples are only used to help understand the method and core idea of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. An optical glass, characterized in that the components of the optical glass, in mass percent, based on the total weight of the glass composition, comprise: 3 to 50.0 percent of SiO 2 0.01 to 15.0 percent of Li 2 O+Na 2 O+K 2 O, baO 6.0-35 wt%, B0.01-15.0 wt% 2 O 3 10% -45% of Nb 2 O 5 ZrO 0.01% -15% 2 TiO 8.5-35.0% 2 5 to 55 percent of La 2 O 3 Bi of 0.01-10.0% 2 O 3 +Gd 2 O 3 +Y 2 O 3 0 to 2.0 percent of CaO,0 to 3.0 percent of SrO and 0 to 10.0 percent of ZnO.
2. The optical glass according to claim 1, wherein the components of the optical glass in mass percent based on the total weight of the glass composition include: 5 to 47.5 percent of SiO 2 0.01 to 12 percentLi 2 O+Na 2 O+K 2 10.5 to 30.5 percent of O,1.1 to 12 percent of BaO and B 2 O 3 12.5 to 37.5 percent of Nb 2 O 5 ZrO 1.0% -13.5% 2 12% -30% of TiO 2 10 to 50.4 percent of La 2 O 3 Bi of 0.05-8.5% 2 O 3 +Gd 2 O 3 +Y 2 O 3 0.01 to 1.7 percent of CaO,0.01 to 2.7 percent of SrO and 0 to 10.0 percent of ZnO.
3. The optical glass according to claim 1, wherein the mass percentages of the components are calculated by substituting formula in mass percentages to obtain Nb 2 O 5 +La 2 O 3 More than or equal to 18.5%, and/or ZrO 2 +SiO 2 +B 2 O 3 Not less than 8%, and/or ZrO 2 +TiO 2 +BaO is more than or equal to 30%; preferably, it is: nb (Nb) 2 O 5 +La 2 O 3 Not less than 23.5.5%, and/or ZrO 2 +SiO 2 +B 2 O 3 More than or equal to 10 percent, and/or ZrO 2 +TiO 2 +BaO≥35.5％。
4. The optical glass according to claim 1, further comprising a fining agent in the glass composition of the optical glass; the clarifier is contained in an amount of 0.01 to 0.5% by mass based on the total weight of the glass composition.
5. An optical glass according to claim 1, wherein the fining agent is at least one of chloride, fluoride and sulfide, preferably chloride.
6. An optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index of greater than 1.9 and/or a visible light transmittance of greater than 85% and/or a density of 4g/cm or less 3 。
7. An optical glass according to any one of claims 1 to 5, wherein the glass liquidus temperature TL of the optical glass is less than 1150 ℃ and/or the glass transition temperature Tg is less than or equal to 620 ℃.
8. A method for producing an optical glass according to any one of claims 1 to 7, comprising:
fully stirring and mixing the raw materials according to the formula proportion to obtain a batch mixture;
melting the batch mixture;
casting the melted mixture into a mould, and annealing to obtain a glass raw sheet;
and processing the glass raw sheet to obtain a glass product.
9. The optical glass according to claim 8, wherein the melting temperature is 1200 to 1500 ℃ for 3 to 8 hours; and/or the annealing temperature is 550-630 ℃ and the annealing time is 1-3 h.
10. Use of an optical glass as defined in any one of claims 1 to 7.
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| CN202211715917.0A CN116239299A (en) | 2022-12-29 | 2022-12-29 | Optical glass and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211715917.0A CN116239299A (en) | 2022-12-29 | 2022-12-29 | Optical glass and preparation method and application thereof |
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| CN116239299A true CN116239299A (en) | 2023-06-09 |
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| CN202211715917.0A Pending CN116239299A (en) | 2022-12-29 | 2022-12-29 | Optical glass and preparation method and application thereof |
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| CN (1) | CN116239299A (en) |
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