CN109320066B - Lanthanum crown optical glass, preparation method thereof and optical element - Google Patents
Lanthanum crown optical glass, preparation method thereof and optical element Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Abstract
The invention provides lanthanum crown optical glass, a preparation method thereof and an optical element, wherein the lanthanum crown optical glass comprises the following components in percentage by weight of the total weight of compounds: SiO 22：18～22％；B2O3：30.1～34％；La2O3：18.5～23％；BaO：5～11.9％；SrO：10.1～15％；CaO：4～8％；ZrO2：1～4％；ZnO：1～5％；Li2O：0.5～3％；Sb2O3: 0.01-0.3%; the above percentages are all weight percentages. The lanthanum crown optical glass has the advantages of low cost, easy softening, low density, good washing resistance and alkali resistance and good transmittance. Furthermore, the invention also provides a preparation method of the lanthanum crown optical glass, and the preparation method has the advantages of easily obtained raw materials, simple and feasible preparation method and suitability for batch production.
Description
Technical Field
The invention relates to lanthanum crown optical glass, a preparation method thereof and an optical element, belonging to the technical field of optical glass.
Background
In recent years, in order to meet the requirements of high-quality digital products on high pixel, small size and portability, lanthanum crown optical glass with the advantages of medium refractive index, low dispersion, low density and the like is increasingly required, because when the product is matched with high-dispersion glass in an optical system, the special dispersion of part of secondary spectrum is favorably counteracted, the resolution of the optical system is improved, and the imaging quality is improved. However, in recent years, La in glass has been used for the purpose of imparting the above properties to glass2O3、Y2O3、Nb2O5And the content of ZnO components is gradually increased, and the defects of small viscosity, high forming difficulty, difficulty in obtaining high-quality stripes, serious crystallization and the like of the glass are caused by excessive components. In addition, in order to reduce the cost, the method is different from the traditional cold processingThe precision mould pressing technology is gradually popularized and applied, but the higher pressing temperature can easily oxidize the mould and damage the surface of the pressing mould, thus reducing the service cycle of the mould and indirectly increasing the pressing production cost.
An optical glass disclosed in patent document CN100431992C, which contains 5 mol% or less of La2O3. In order to achieve a predetermined refractive index ndLess La2O3The content can indirectly cause Gd2O3、Y2O3、Nb2O5Increased content of Gd2O3The increase in content undoubtedly increases the cost of the glass and impairs the market competitiveness of the product, Y2O3The addition of (2) increases the glass cost and increases the tendency of the glass to devitrify, and Nb2O5When the content is increased, the dispersion of the glass is greatly increased and the refractive index n is increaseddThe preset Abbe number upsilon is difficult to realize under the premise of determinationd。
An optical glass disclosed in patent document CN1313405C, which contains 4 mol% or less of S (SrO + CaO). An excessively low content of S (SrO + CaO) is disadvantageous in improving the coloration, transmittance and washing resistance R of the glassP(S), alkali resistance ROH (S).
The optical glass disclosed in patent document CN103771705A, which contains 15% or less of SiO2And 30% or less of B2O3And more than 25% BaO. Too little B2O3Will give the glass melting behaviour and washing resistance RP(S), alkali resistance ROH (S) becomes poor, when SiO is formed2And B2O3When both are small, the total amount of the network-forming material in the glass is small, and the devitrification performance of the glass is drastically deteriorated. Too high a BaO increases the density and leads to devitrification and washing resistance R of the glassP(S), the alkali resistance ROH (S) gradually worsens.
Patent document CN1155528C discloses an optical glass containing 35% or more of B2O310% or more of CaO, 0.5% or less of Li2And O. Higher B2O3The content of the glass is such that the viscosity of the glass becomes smallIncreased difficulty of forming, gradually deteriorated devitrification resistance, higher CaO content which results in washing resistance RP(S), poor alkali resistance ROH (S), less Li2The O content makes the glass transition temperature too high.
Patent document CN102311228A discloses an optical glass containing 30% or less of B2O315% or less of La2O3And more than 20% BaO. Less B2O3Will give the glass melting behaviour and washing resistance RP(S), alkali resistance ROH(S) is deteriorated, less La2O3The required n is not easily realizedd、υdMore BaO is required to improve the devitrification and washing resistance R of the glassP(S), alkali resistance ROH(S) gradually worsens and increases the density.
In addition, the optical glasses disclosed in patents CN1903760A, CN1666967A, CN1903762A, CN101445322A, CN101215083A, CN1303024C, CN101362629A, etc. are obviously different from the present invention in composition, application field and use, attention and required optical performance, etc.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the invention firstly provides a refractive index ndBetween 1.62 and 1.68, Abbe number upsilondBetween 56 and 60 lanthanum crown optical glass. The lanthanum crown optical glass has the characteristics of low cost, easy softening, low density, good washing resistance and alkali resistance, good transmittance and suitability for production.
Furthermore, the invention also provides a preparation method which is easy to obtain raw materials and suitable for batch production.
Further, the present invention also provides an optical element comprising the lanthanum crown optical glass of the present invention.
Means for solving the problems
The invention provides lanthanum crown optical glass, which comprises the following components in percentage by weight of the total weight of compounds:
SiO2：18～22％；
B2O3：30.1～34％；
La2O3：18.5～23％；
BaO：5～11.9％；
SrO：10.1～15％；
CaO：4～8％；
ZrO2：1～4％；
ZnO：1～5％；
Li2O：0.5～3％；
Sb2O3：0.01～0.3％；
the above percentages are all weight percentages.
The lanthanum crown optical glass according to the present invention, wherein the SiO is contained in an amount of the compound based on the total weight of the compound2The addition amount of (A) is 19-21.5%; and/or, said B2O3The addition amount of (A) is 30.5-33%; and/or, the La2O3The addition amount of (A) is 19-21.5%; and/or the addition amount of BaO is 7-11%; and/or the addition amount of the SrO is 10.1-13%; and/or the addition amount of CaO is 4-7%; and/or, the ZrO2The addition amount of (A) is 1-3.5%; and/or the addition amount of ZnO is 1-4%; the Li2The adding amount of O is 0.5-2.5%; the Sb2O3The addition amount of (A) is 0.01-0.1%.
The lanthanum crown optical glass according to the present invention, wherein the SiO is contained in an amount of the compound based on the total weight of the compound2In a ratio of (B) to the total amount of B2O3Content ratio of (A) to (B) SiO2/B2O30.55 to 0.75.
The lanthanum crown optical glass according to the present invention has a formula (E) of 20 to 29% by weight of the total compound.
The lanthanum crown optical glass according to the present invention is characterized in that the ratio of the content of BaO to the content of SrO, BaO/SrO, is 1 or less, based on the total weight of the compounds.
The lanthanum crown optical glass according to the present invention, whereinRefractive index n of the lanthanum crown optical glassdBetween 1.62 and 1.68, Abbe number upsilondBetween 56 and 60.
The lanthanum crown optical glass of the invention is characterized in that the transition temperature Tg of the lanthanum crown optical glass is below 610 ℃, and the sag temperature Ts is below 660 ℃; and/or the lanthanum crown optical glass has the density of 3.60g/cm3The following; and/or, the washing resistance R of the lanthanum crown optical glassP(S) is 1-3 grade, and the alkali resistance R of the lanthanum crown optical glassOH(S) is 1-stage.
The lanthanum crown optical glass according to the present invention, wherein the lanthanum crown optical glass has a degree of coloration λ80/λ5λ of (2)80At 355nm or less, lambda5Below 275 nm; and/or the lanthanum crown optical glass has an internal transmittance at 450nm of 99.5% or more and an internal transmittance at 360nm of 93% or more.
The invention also provides a preparation method of the lanthanum crown optical glass, which comprises the step of mixing the components of the lanthanum crown optical glass.
The invention also provides an optical element comprising a lanthanum crown optical glass according to the invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The lanthanum crown optical glass has the advantages of low cost, easy softening, low density, good washing resistance and alkali resistance and good transmittance.
Furthermore, the invention also provides a preparation method of the lanthanum crown optical glass, and the preparation method has the advantages of easily obtained raw materials, simple and feasible preparation method and suitability for batch production.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
In the lanthanum crown optical glass produced by the present invention, each component is selected in the above-mentioned amounts for the reasons described below. As described below, the contents of the respective components are expressed in weight percent (wt%).
In the present invention, SiO2Can improve the high-temperature viscosity of the glass, is a glass network generation body in the glass, and can improve the devitrification resistance and the chemical stability of the glass and the mechanical property of the glass by adding a proper amount of the glass. In the present invention, when SiO is used, based on the total weight of the compound2When the content of (b) is less than 18%, the effect is not sufficiently remarkable; when SiO is present2When the content of (b) is more than 22%, the glass is not easily melted, the risk of occurrence of non-melted foreign matter is increased, the transition temperature Tg is increased, and the glass press molding is not facilitated, and SiO2Too high a content of a washing resistance RP(S), alkali resistance ROHThere is also a tendency for (S) to deteriorate. Therefore, SiO2The content of (b) should be controlled between 18% and 22%, preferably between 19% and 21.5%, for example: SiO 22The content of (b) may be 18.5%, 19.5%, 20%, 20.5%, 21%, etc.
In the present invention, B2O3In glass, also a network forming body of glass, and B2O3Can also improve the melting performance of the glass and improve the washing fastness R of the glassP(S). When B is present in the composition, based on the total weight of the compound2O3When the content is less than 30.1%, the melting property of the glass is deteriorated and R is improvedPThe effect of (S) is not sufficiently pronounced; when B is2O3When the content is more than 34%, the refractive index of the glass is not easy to achieve the object of the present invention, it is difficult to obtain desired optical properties, and the viscosity of the glass is decreased to increase the molding difficulty. Therefore, in the present invention, B2O3Should be contained in an amountThe content is controlled to be between 30.1 and 34 percent, and preferably between 30.5 and 33 percent; for example: b is2O3The content of (b) may be 31%, 31.5%, 32%, 32.5%, 33.5%, etc.
In the present invention, when SiO is used2Content of (A) and (B)2O3Content ratio of (A) to (B) SiO2/B2O3Larger, will result in SiO2Increases the risk of the occurrence of undissolved foreign bodies and raises the dispersion and thus the refractive index ndAnd Abbe number upsilondThe matching property of (2) becomes poor when SiO is used2Content of (A) and (B)2O3Content ratio of (A) to (B) SiO2/B2O3Smaller, then B will be2O3The volatile loss of (A) is gradually increased, which is not favorable for the stability of the optical performance of the product. Therefore, in the present invention, the SiO is present in an amount based on the total weight of the compound2In a ratio of (B) to the total amount of B2O3Content ratio of (A) to (B) SiO2/B2O30.55 to 0.75, preferably 0.6 to 0.7, for example, the SiO2In a ratio of (B) to the total amount of B2O3Content ratio of (A) to (B) SiO2/B2O3May be 0.58, 0.62, 0.65, 0.68, 0.72, etc.
La2O3Has relatively high refractive index and low dispersion, is one of the main components of lanthanide glass, and has optical characteristics capable of being flexibly mixed with ZnO and ZrO2、RO、R2O together adjust the optical constants of the glass, and the combination adjustment mode is more beneficial to matching the refractive index and the dispersion of the optical glass. In the present invention, La2O3Can be mixed with ZnO and ZrO2、BaO、SrO、Li2O-match using a total or partial replacement of expensive Y2O3、Gd2O3、Ta2O5The components are beneficial to reducing the density of the glass while realizing the reduction of the product cost.
When La is present, based on the total weight of the compound2O3When the content is less than 18.5%, the advantages are difficult to realize; and La2O3When the content is more than 23 percentThe devitrification property of the glass is gradually deteriorated. Therefore, La2O3The content of (A) should be controlled between 18.5% and 23%, preferably between 19% and 21.5%; for example: la2O3The content of (b) may be 19%, 19.5%, 20%, 20.5%, 21%, 22%, 22.5%, etc.
The function of BaO in glass is similar to that of SrO and CaO, but there is a difference in the optimum range of the amount to be introduced.
In the present invention, the addition of BaO within a certain range can improve the devitrification property, the coloring degree and the transmittance of the glass. When the BaO content is less than 5% by total weight of the compound, the above-mentioned effect is not significant enough; when the content of BaO is more than 11.9%, the tendency of devitrification of the glass is increased and the density is increased, and further, the increase of the content of BaO is responsible for the resistance to washing RP(S), alkali resistance ROHThere is also a tendency for (S) to deteriorate. Therefore, the content of BaO should be controlled between 5-11.9%, preferably 7-11%, for example: the content of BaO may be 5.5%, 6%, 6.5%, 7.5%, 8%, 8.5%, 9, 9.5%, 10%, 10.5%, 11.5%, or the like.
Partial replacement of BaO with SrO in the disclosed glass system facilitates a reduction in glass density and may mitigate the resistance to washing RP(S), alkali resistance ROHDegree of deterioration of (S). When the content of SrO is less than 10.1% by total weight of the compound, the above effect is not sufficiently significant; when the content of SrO is more than 15%, the tendency of glass to devitrify increases. Therefore, the content of SrO should be controlled between 10.1% and 15%, preferably between 10.1% and 13%, for example: the SrO content may be 10%, 10.5%, 11.5%, 12%, 12.5%, 13.4%, 14.5%, etc.
In the invention, CaO is added in a certain range to improve the crystallization performance and the transmittance of the glass, and the CaO is used for partially replacing BaO, which is beneficial to reducing the density of the glass. When the CaO content is less than 4% by total weight of the compound, the above-mentioned effect is not sufficiently significant; when the CaO content is more than 8%, the tendency of the glass to devitrify increases. Therefore, in the present invention, the content of CaO is controlled to be between 4% and 8%, preferably between 4% and 7%, and for example, the content of CaO may be 4.5%, 5%, 5.5%, 6.5%, or the like.
When the sigma (BaO + SrO + CaO) is too low based on the total weight of the compound, the devitrification property of the glass is deteriorated and the coloring degree and transmittance of the glass are difficult to achieve the desired effects, and when the sigma (BaO + SrO + CaO) is too high, the resistance to washing R is deterioratedP(S), alkali resistance ROH(S) it is difficult to achieve the desired effect. Therefore, in the present invention, Σ (BaO + SrO + CaO) is preferably 20 to 29%, more preferably 21 to 28%, based on the total weight of the compound, and for example, Σ (BaO + SrO + CaO) may be 22%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 27%, or the like.
When the ratio of the content of BaO to the content of SrO, based on the total weight of the compound, BaO/SrO is too high, the density of the glass increases and the resistance to washing RP(S), alkali resistance ROH(S) also deteriorates. Therefore, in the present invention, the ratio of the content of BaO to the content of SrO, BaO/SrO, is 1 or less, preferably between 0.4 and 0.9, based on the total weight of the compound, for example the ratio of the content of BaO to the content of SrO, BaO/SrO may be 0.2, 0.3, 0.5, 0.6, 0.7, 0.8, etc.
In the present invention, ZrO2Has the function of improving devitrification resistance, can also play the roles of improving the refractive index and reducing dispersion in most lanthanum crown optical glasses, and is an essential additive component in the invention. ZrO based on the total weight of the compound2When the content is less than 1%, the effect is not obvious enough; and ZrO2When the content is more than 4%, the devitrification property of the glass is gradually deteriorated, the melting temperature is increased, and the resistance to washing R is increasedP(S), alkali resistance ROH(S) also has certain deterioration effect. Therefore, ZrO2The content of (B) is controlled to be 1% to 4%, preferably 1% to 3.5%, for example, ZrO2The content of (b) may be 1.5%, 2%, 2.5%, 3%, etc.
In the present invention, ZnO can reduce the devitrification tendency of the glass, lower the transition temperature Tg and the sag temperature Ts of the glass, and improve the washing resistance RP(S), alkali resistance ROHThe effect of (S) is excellent.When the content of ZnO is less than 1% by weight based on the total weight of the compound, the effect is not sufficiently significant; when the content of ZnO is more than 5%, the viscosity of the glass gradually decreases and the acid resistance gradually deteriorates. Therefore, the content of ZnO should be controlled to be between 1% and 5%, preferably between 1% and 4%, and for example, the content of ZnO may be 1.5%, 2%, 2.5%, 3%, 3.5%, 4.5%, or the like.
In the present invention, Li2O has effective fluxing action in the glass, can effectively reduce the transition temperature Tg and the sag temperature Ts of the glass, and is added in a certain range to improve the washing fastness RP(S), alkali resistance ROHThe (S) effect is obvious. Based on the total weight of the compound, Li2When the O content is less than 0.5%, the effect is not sufficiently obvious; li2Washing resistance R when the O content is more than 3%P(S), alkali resistance ROHThe effect of (S) is rather worsened and too much Li is present2O destroys the glass network and deteriorates the devitrification performance of the glass. Therefore, Li2The content of O should be controlled between 0.5% and 3%, preferably between 0.5% and 2.5%, for example: li2The content of O may be 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.8%, etc.
Sb2O3Is added as a defoaming agent, but the content thereof is sufficient to be within 0.3%, and Sb is added2O3If it exceeds 0.3%, the glass tends to have poor coloring degree and internal transmittance. Thus Sb2O3The content of the components is limited to 0.01-0.3%, preferably 0.01-0.1%.
In the present invention, TiO is preferably not contained2、Gd2O3、Y2O3、Na2O、K2O、MgO、Al2O3And/or Nb2O5And the like.
In order to ensure that the aim of the invention is achieved, the optical glass provided by the invention can not artificially introduce other elements except the components, namely the total content of the components is 100 percent.
In the composition of lanthanum crown optical glasses, La2O3、Ta2O5、Gd2O3、Al2O3、Y2O3The effects of the components have similarity, and the optical glass with excellent performance is obtained by adjusting the reasonable proportion of other components. But La2O3、Ta2O5、Gd2O3、Y2O3The price of (c) is different, for example: y is2O3Market price of La is about2O320% higher, and Gd2O3Has a market price of La2O3More than 2 times of Ta2O5Price is La2O3More than 15 times of the total weight of the composition.
However, the present invention is achieved by using La2O3Wholly or partially replacing expensive Y2O3、Gd2O3And Ta2O5The components are reasonably mixed with other components to ensure that the performance of the glass is not deteriorated and the stable mass production can be realized, thereby obtaining the lanthanum crown optical glass. Refractive index (n) of the lanthanum crown optical glassd) Between 1.62 and 1.68, Abbe number (upsilon)d) 56-60, low cost, easy softening, low density, good washing resistance and alkali resistance, good transmittance and suitability for production.
In the invention, the transition temperature Tg of the lanthanum crown optical glass is below 610 ℃, and the sag temperature Ts is below 660 ℃; and/or the density of the optical glass is 3.60g/cm3The following; and/or, the washing resistance R of the lanthanum crown optical glassP(S) is 1-3 grade, and the alkali resistance R of the lanthanum crown optical glassOH(S) is 1-stage.
In the present invention, the lanthanum crown optical glass has a coloring degree λ80/λ5λ of (2)80At 355nm or less, lambda5Below 275 nm; and/or the lanthanum crown optical glass has an internal transmittance at 450nm of 99.5% or more and an internal transmittance at 360nm of 93% or more.
The invention also provides an optical element comprising a lanthanum crown optical glass according to the invention.
The invention also provides a method for making lanthanum crown optical glass according to the invention, which includes the step of mixing the components of the lanthanum crown optical glass.
Specifically, the raw materials are weighed according to a specified proportion, mixed into a batch, smelted in a crucible made of platinum at the temperature of 1220-1270 ℃, and after the raw materials are melted into molten glass, the temperature is raised to 1290-1340 ℃, and a stirrer made of platinum materials is started to stir and homogenize, wherein the stirring time is controlled to be 5-10 hours. And after stirring, heating to 1340-1380 ℃, preserving heat for 5-10 hours, clarifying to enable bubbles to float sufficiently, then cooling to 1050-1150 ℃, pouring or leaking into a forming die or performing compression molding, and finally annealing and processing to obtain the lanthanum crown optical glass or the optical element.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The components of examples 1 to 11 in tables 3 to 4 were weighed according to the specified proportions, mixed into a batch, melted in a crucible made of platinum at 1250 ℃, and after the raw materials were melted into molten glass, the temperature was raised to 1320 ℃, and a stirrer made of platinum material was started to stir and homogenize, and the stirring time was controlled at 8 hours. After stirring, heating to 1360 ℃, keeping the temperature for 8h, clarifying to enable bubbles to float sufficiently, then cooling to 1100 ℃, pouring or leaking into a forming die or carrying out compression molding, and finally annealing and processing to obtain the lanthanum crown optical glass.
Comparative example
The lanthanum crown optical glasses of comparative examples a to C were obtained by weighing the raw materials corresponding to the components of comparative examples a to C in table 4 in the prescribed proportions and preparing the same as in examples 1 to 11.
Performance testing
1. Refractive index ndAbbe number upsilond
Refractive index (n)d) And Abbe number (. nu.)d) The test (2) is carried out according to the test method of GB/T7962.1-2010 standard.
2. Transition temperature Tg and sag temperature Ts
The transition temperature (Tg) and the sag temperature (Ts) were measured according to the test method of GB/T7962.16-2010 standard.
3. Density p
The density was determined according to the test method of GB/T7962.20-2010 standard.
4. Washing resistance RP(S)
Washing resistance RP(S) (surface method) the test method was: six-side polished 35mm × 35mm × 8mm samples were immersed in Na having a constant temperature of 50 ℃ + -3 ℃ and a concentration of 0.01mol/L and sufficiently stirred5P3O10Aqueous solution for 1 hour. In terms of average value of leaching mass per unit area, unit mg/(cm)2H) the washing resistance stability RP (S) of the optical glasses is divided into five stages, as shown in Table 1:
TABLE 1
5. Alkali resistance ROH(S)
Alkali resistance ROH(S) (surface method) the test method was: a sample having six polished dimensions of 40X 5mm was immersed in an aqueous solution of sodium hydroxide with a constant temperature of 50 ℃. + -. 3 ℃ and a concentration of 0.01mol/L for 15 hours while stirring sufficiently. In terms of average value of leaching mass per unit area, unit mg/(cm)215h) stability of the alkali resistance of the lanthanum crown optical glass ROH(S) is divided into five stages, as shown in Table 2:
table 2:
6. degree of coloration lambda80/λ5
Degree of coloration lambda80/λ5Middle lambda80Means the wavelength corresponding to a glass transmittance of 80% (sample thickness 10. + -. 0.1mm), lambda5The wavelength corresponding to the glass transmittance of 5% is referred to. The optical glass is measured according to the "optical glass coloring degree measuring method" of the Japan glass industry Association, JOGIS 02-2003.
7. Internal transmittance τ10
Internal transmittance τ of the present invention10Means that the internal transmittance test values of the glass with the thickness of 10 +/-0.1 mm at the wavelengths of 360nm and 450nm are tested according to the GB/T7962.12-2010 standard.
The refractive index n of lanthanum crown optical glasses prepared in examples 1 to 11 and comparative examples A to CdAbbe number upsilondTransition temperature Tg, sag temperature Ts, density rho, and coloring degree lambda80/λ5Washing resistance RP(S), alkali resistance ROH(S) and internal transmittance τ10Listed in tables 3-4; the data measured for comparative examples A-C are shown in Table 4.
TABLE 3
TABLE 4
As can be seen from tables 3 to 4, the lanthanum crown optical glasses of examples 1 to 11 of the present invention have a transition temperature Tg of 610 ℃ or lower, a sag temperature Ts of 660 ℃ or lower, and a density of 3.60g/cm3Following, washing resistance RP(S) is grade 1-3, alkali resistance ROH(S) is 1-stage. The color degree lambda of the lanthanum crown optical glass80/λ5λ of (2)80At 355nm or less, lambda5Below 275 nm; the lanthanum crown optical glass has an internal transmittance at 450nm of 99.5% or more and an internal transmittance at 360nm of 93% or more. Therefore, the lanthanum crown optical glass has the characteristics of excellent performance, easy softening, low density, good washing resistance and alkali resistance, good transmittance and the like.
SiO in comparative example A2Content of (A) and (B)2O3In spite of the resistance to washing RP(S), alkali resistance ROH(S) is less deteriorated, but its Li is excessive2Component O is the resistance to washing RP(S), alkali resistance ROH(S) has a large deterioration effect. And SiO in comparative example A2、B2O3、La2O3、BaO、SrO、ZnO、Li2O、Sb2O3The content of the components is not in the scope of the invention, SiO2/B2O3The values of (BaO + SrO + CaO) and (BaO/SrO) are not within the range of the present invention, and the glass has a washing resistance RP(S), alkali resistance ROH(S) is inferior to examples 1 to 11 of the present application.
Comparative example B contains a small amount of TiO2Albeit TiO2Can be used to adjust nd、υdBut a small amount of the additive causes deterioration of the coloring degree and transmittance, and B in comparative example B2O3、La2O3、SrO、ZrO2、ZnO、Li2The content of O and the like is out of the range of the present invention, SiO2/B2O3Sigma (BaO + SrO + CaO), BaO/SrO values are not within the scope of the present invention, and n of the glass is not within the scope of the present inventiond、υdNot in the scope of the present invention, λ 80/λ 5, internal transmittance τ10Compared to examples 1-11 of the present application.
Comparative example C does not contain Li2O component, and B2O3Low ZnO content, high transformation temperature Tg and sag temperature Ts, unfavorable extension of the service life of the die in profiling production, and introduction of more Gd2O3The components increase the density and are also bound toThe cost of the product is greatly increased. In comparative example C, SrO, CaO and Li2O、Sb2O3The contents of the components are out of the range of the present invention, and the sigma (BaO + SrO + CaO), BaO/SrO values are out of the range of the present invention, the glass has a lower transition temperature Tg and a lower sag temperature Ts than those of examples 1 to 11 of the present application.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The lanthanum crown optical glass is characterized by comprising the following components in percentage by weight of the total compound:
SiO2：18～22％；
B2O3：30.1～34％；
La2O3：18.5～23％；
BaO：5～11.9％；
SrO：10.1～15％；
CaO：4～8％；
ZrO2：1～4％；
ZnO：1～5％；
Li2O：0.5～3％；
Sb2O3：0.01～0.3％；
the above percentages are all weight percentages.
2. The lanthanum crown optical glass according to claim 1, wherein the SiO is present in the glass as a whole in weight percent based on the total compound2The addition amount of (A) is 19-21.5%; and/or, said B2O3The addition amount of (A) is 30.5-33%; and/or, the La2O3The addition amount of (A) is 19-21.5%; and/or the addition amount of BaO is 7-11%; and/or the addition amount of the SrO is 10.1-13%; and/or the addition amount of CaO is 4-7%; and/or, the ZrO2The addition amount of (A) is 1-3.5%; and/or the addition amount of ZnO is 1-4%; the Li2The adding amount of O is 0.5-2.5%; the Sb2O3The addition amount of (A) is 0.01-0.1%.
3. The lanthanum crown optical glass according to claim 1 or 2, characterized in that the SiO is present in the glass by weight of the total compound2In a ratio of (B) to the total amount of B2O3Content ratio of (A) to (B) SiO2/B2O30.55 to 0.75.
4. The lanthanum crown optical glass according to claim 1 or 2, wherein Σ (BaO + SrO + CaO) is 20 to 29% by weight based on the total weight of the compound.
5. The lanthanum crown optical glass according to claim 1 or 2, characterized in that the ratio BaO/SrO of the content of BaO to the content of SrO is less than or equal to 1, based on the total weight of the compounds.
6. The lanthanum crown optical glass of claim 1 or 2, wherein the lanthanum crown optical glass has a refractive index ndBetween 1.62 and 1.68, Abbe number upsilondBetween 56 and 60.
7. The lanthanum crown optical glass according to claim 1 or 2, characterized in that the lanthanum crown optical glass has a transition temperature Tg below 610 ℃ and a sag temperature Ts below 660 ℃; and/or the lanthanum crown optical glass has the density of 3.60g/cm3The following; and/or, the washing resistance R of the lanthanum crown optical glassP(S) is 1-3 grade, and the alkali resistance R of the lanthanum crown optical glassOH(S) is 1-stage.
8. According to claimThe lanthanum crown optical glass according to claim 1 or 2, characterized in that the lanthanum crown optical glass has a degree of coloration λ80/λ5λ of (2)80At 355nm or less, lambda5Below 275 nm; and/or the lanthanum crown optical glass has an internal transmittance at 450nm of 99.5% or more and an internal transmittance at 360nm of 93% or more.
9. A method of making lanthanum crown glass according to any of claims 1 to 8 including the step of mixing the components of the lanthanum crown glass.
10. An optical element comprising a lanthanum crown optical glass according to any of claims 1 to 8.
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|---|---|---|---|---|
| CN1198414A (en) * | 1997-03-25 | 1998-11-11 | 株式会社小原 | Optical glass with negative anomalous dispersion |
| CN1244851A (en) * | 1997-01-29 | 2000-02-16 | 康宁股份有限公司 | Glasses with very high refractive index |
| US20070249482A1 (en) * | 2001-08-02 | 2007-10-25 | 3M Innovative Properties Company | Al2O3-RARE EARTH OXIDE-ZrO2/HfO2 MATERIALS, AND METHODS OF MAKING AND USING THE SAME |
| WO2011046156A1 (en) * | 2009-10-15 | 2011-04-21 | 旭硝子株式会社 | Glass for diffusion layer in organic led element, and organic led element utilizing same |
| JP2016121035A (en) * | 2014-12-24 | 2016-07-07 | 株式会社オハラ | Optical glass, preform and optical element |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244851A (en) * | 1997-01-29 | 2000-02-16 | 康宁股份有限公司 | Glasses with very high refractive index |
| CN1198414A (en) * | 1997-03-25 | 1998-11-11 | 株式会社小原 | Optical glass with negative anomalous dispersion |
| US20070249482A1 (en) * | 2001-08-02 | 2007-10-25 | 3M Innovative Properties Company | Al2O3-RARE EARTH OXIDE-ZrO2/HfO2 MATERIALS, AND METHODS OF MAKING AND USING THE SAME |
| WO2011046156A1 (en) * | 2009-10-15 | 2011-04-21 | 旭硝子株式会社 | Glass for diffusion layer in organic led element, and organic led element utilizing same |
| JP2016121035A (en) * | 2014-12-24 | 2016-07-07 | 株式会社オハラ | Optical glass, preform and optical element |
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