CN110835232B - Optical glass, glass preform or optical element prepared from optical glass, and optical instrument - Google Patents

Optical glass, glass preform or optical element prepared from optical glass, and optical instrument Download PDF

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CN110835232B
CN110835232B CN201810943256.4A CN201810943256A CN110835232B CN 110835232 B CN110835232 B CN 110835232B CN 201810943256 A CN201810943256 A CN 201810943256A CN 110835232 B CN110835232 B CN 110835232B
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optical glass
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CN110835232A (en
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孙伟
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Optics & Photonics (AREA)
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Abstract

The invention discloses optical glass, a glass prefabricated member or an optical element prepared from the optical glass and an optical instrument. The optical glass comprises the following components in percentage by mass relative to the total mass of the glass with the composition converted by oxides: b 2 O 3 ：5～25％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0～10％，Ta 2 O 5 :0 to 10% and La in a total amount of 50 to 75% 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 ，La 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625. By applying the technical scheme of the invention, the components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass has excellent performance.

Description

Optical glass, glass preform or optical element prepared from optical glass, and optical instrument
Technical Field
The invention relates to the technical field of optical glass, in particular to optical glass, a glass prefabricated member or an optical element prepared from the optical glass and an optical instrument.
Background
At present, the development of digital photographing apparatuses, image pickup apparatuses, projection apparatuses, and the like has required higher optical elements, which requires the development and production of optical glasses with higher performance. Among them, a lens formed of a high refractive index low dispersion optical glass is combined with a lens formed of a high refractive index high dispersion optical glass, and chromatic aberration can be corrected to miniaturize an optical system, and particularly, a high refractive index low dispersion optical glass having a refractive index nd of more than 1.87 and an abbe number vd of more than 38.0 is increasingly demanded in the market.
The basic system of the formula for meeting the optical index is that B-La-Zr-Ta is good, and glass is easy to form, thus being beneficial to production. In addition, in general, more rare earth oxides are required to be introduced into a high-refraction low-dispersion glass formula system to improve the refractive index of the glass, but in different formula systems, more lanthanide oxides are introduced to influence the glass forming property, if the content is more, the glass is easy to crystallize, the crystallization upper limit temperature is higher, and the difficulty is brought to mass production process manufacturing.
Disclosure of Invention
The invention aims to provide optical glass, a glass prefabricated member or an optical element prepared from the optical glass and an optical instrument, and aims to solve the technical problem that high-refraction low-dispersion optical glass in the prior art is difficult to produce in volatile transmission amount.
In order to achieve the above object, according to one aspect of the present invention, there is provided an optical glass. The optical glass comprises the following components in percentage by mass relative to the total mass of the glass with the composition converted by oxides: b is 2 O 3 ：5～25％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0～10％，Ta 2 O 5 :0 to 10% and La in a total amount of 50 to 75% 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 ，La 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625.
Further, the optical glass further comprises a glass selected from the group consisting of ZnO, baO, caO, srO, mgO, WO 3 、Sb 2 O 3 、Li 2 O、Na 2 O and K 2 O, and the content is as follows: znO:0 to 15%, baO:0 to 10 percent; caO:0 to 10 percent; srO:0 to 10 percent; mgO:0 to 10%, WO 3 ：0～10％；Sb 2 O 3 ：0～1％，Li 2 O、Na 2 O and K 2 The total amount of O is 0 to 10 percent.
Further, the optical glass is composed of B in mass percentage with respect to the total mass of the glass of the composition in terms of oxides 2 O 3 ：5～25％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0～10％，ZnO：0～15％，BaO：0～10％，CaO：0～10％，SrO：0～10％，MgO：0～10％，WO 3 ：0～10％，Ta 2 O 5 :0 to 10 percent of Li and the total amount of Li is 0 to 10 percent 2 O、Na 2 O and K 2 O，Sb 2 O 3 :0 to 1% and La in a total amount of 50 to 75% 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 Composition of, wherein, la 2 O 3 With Gd 2 O 3 La by weight of 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625.
Further, the optical glass includes, in terms of mass percentage content, with respect to the total mass of the glass of the composition in terms of oxides: b is 2 O 3 ：8～22％，Nb 2 O 5 ：5.6～10％，SiO 2 ：3～10％，ZrO 2 ：3～12％，TiO 2 ：0.5～7％，Ta 2 O 5 : 5-10% and/or 55-70% of La in total 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 。
Further, la 2 O 3 /Gd 2 O 3 Is 1.3 to 1.6.
Further, la 2 O 3 /Gd 2 O 3 Is 1.4 to 1.5.
Further, the optical glass does not contain Y 2 O 3 And/or WO 3 。
Further, nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 0.75 to 2.
Further, nb 2 O 5 /SiO 2 Is 1 to 1.5.
Further, the upper limit temperature of devitrification of the optical glass is less than 1350 ℃, preferably less than 1300 ℃.
Further, the refractive index nd of the optical glass is > 1.87, preferably nd > 1.88; the Abbe number vd is > 38.0, preferably vd > 39.0.
Further, the water-resistant stability Dw of the optical glass is above grade 3, preferably above grade 2, more preferably above grade 1; stability against acid action D A At 3 or more, preferably at 2 or more, more preferably at 1. Further, the striae of the optical glass are grade C or more, preferably grade B or more, more preferably grade a; the degree of bubbling is at least class A, preferably A 0 More than class A, more preferably A 00 And (4) stage.
According to another aspect of the present invention, there is provided a glass preform or an optical element. The glass preform or the optical element is produced from any of the above optical glasses.
According to a further aspect of the present invention there is provided an optical instrument comprising an optical element, the optical element being any one of the optical elements described above.
By applying the technical scheme of the invention, the components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass can obtain high-refraction low-dispersion optical glass with devitrification resistance and excellent performance, and the optical glass is easy to produce in mass production.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In the present specification, unless otherwise specified, the contents of the respective components are all expressed in mass% with respect to the total mass of the glass in terms of oxides. The "composition in terms of oxides" refers to the composition of each component contained in the glass, which is expressed by assuming that all raw materials as the glass constituent components of the present invention are decomposed and converted into oxides during melting, and the total mass of the generated oxides is 100 mass%.
The basic role of each component in the optical glass will be described below, but the synergistic effect or unexpected effect of the components due to the specific content ratio is not unduly limited.
Glass composition
B 2 O 3 Is a skeleton component of the glass, and has the functions of improving the meltability, resisting devitrification and reducing the glass in the inventionThe effect of glass dispersion. However, when the amount of incorporation exceeds 25%, the glass stability is lowered and the refractive index is lowered, and when the amount of incorporation is less than 5%, the glass meltability is lowered and the optical constants required in the present invention are not obtained. Thus, B of the present invention 2 O 3 In an amount of 5 to 25%, preferably B 2 O 3 The content is 8-22%.
Nb 2 O 5 The glass also has the effect of improving the crystallization resistance and chemical durability of the glass in order to improve the refractive index and dispersion components. When Nb 2 O 5 When the content is less than 2%, the above effects cannot be achieved; if the content exceeds 15%, the glass dispersion is improved, the coloring tendency is increased, the optical characteristics of the glass of the present invention cannot be achieved, and the devitrification resistance of the glass is deteriorated. Nb in the invention 2 O 5 The content is 2 to 15%, preferably Nb 2 O 5 The content is 5.6-10%.
SiO 2 The component constituting the glass skeleton has the effects of improving resistance to devitrification and increasing the operating temperature range, and also has the effects of improving chemical stability of glass, improving thermal stability of glass, and the like. If the content exceeds 15%, the glass is deteriorated in meltability and the refractive index required in the present invention cannot be obtained. SiO in the invention 2 The content is 0.5 to 15%, preferably SiO 2 The content is 3-10%.
ZrO 2 A component for improving refractive index and stability. Glass is formed as an intermediate oxide, and therefore, it also has an effect of improving resistance to devitrification and chemical stability. ZrO (zirconium oxide) 2 When the content of (A) is less than 1%, the above-mentioned intended effect cannot be obtained, and when ZrO is contained in the composition 2 When the content of (b) exceeds 15%, devitrification tendency becomes strong and vitrification tends to become difficult. ZrO in the invention 2 The content is 1 to 15%, preferably ZrO 2 The content is 3-12%.
TiO 2 Also has the function of improving the refractive index of the glass, can participate in the formation of a glass network, and leads the glass to be more stable by introducing a proper amount. However, if the amount is excessively contained, the glass dispersion is remarkably increased, and the transmittance of the glass in a short wavelength portion of a visible light region is lowered, whereby the glass is coloredThe tendency increases. In the present invention, tiO 2 The content is 0 to 10%, preferably 0.5 to 7%.
La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 Are the main components for increasing the refractive index of the glass, and can increase the refractive index without significantly increasing the dispersion. The addition of a certain amount of the rare earth oxide can reduce the crystallization upper limit temperature, improve the devitrification resistance of the glass, improve the chemical stability, and prevent the generation of glass bubbles in the melting process, so that the La in the high-refraction low-dispersion glass formula system of the invention 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total content is not less than 50 percent and not more than 75 percent, so as to ensure the realization of the technical effects and achieve the aim of the invention; a preferred range is 55 to 70%, more preferably 60 to 67%. However, under normal conditions, the more lanthanide oxides are introduced, the glass forming property is also influenced, if the content is high, the glass is easy to crystallize, the crystallization upper limit temperature is high, and difficulty is brought to mass production process manufacturing; therefore, the content of lanthanide oxide with high-refraction low-dispersion performance can be generally below 60 percent to ensure that the glass is not easy to crystallize, and La oxide is controlled in the high-refraction low-dispersion glass of the invention 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 1.28 to 1.625, the content of the lanthanide oxide can be below 60 percent and above 60 percent, the crystallization upper limit temperature of the glass can still be ensured not to rise, the crystallization upper limit temperature is lower than 1350 ℃, preferably lower than 1300 ℃, more preferably lower than 1280 ℃, the glass forming property of the components can be ensured to be better, glass bubbles are not easy to generate in the melting process, and good optical property, forming property and the like are also ensured, preferably, la 2 O 3 /Gd 2 O 3 1.3 to 1.6; more preferably, la 2 O 3 /Gd 2 O 3 Is 1.4 to 1.5.
While ZnO can adjust the refractive index and dispersion of the glass, and a suitable amount of ZnO can improve the stability or melting property of the glass and press formability, when the content is too high, the refractive index decreases, which does not meet the requirements of the present invention, and the devitrification resistance of the glass decreases and the upper limit temperature of devitrification increases. The ZnO content of the present invention is therefore from 0 to 15%, preferably from 0 to 10%, more preferably from 0 to 5%.
Ta 2 O 5 Is a component for increasing the refractive index and resistance to devitrification of the glass, and is Ta 2 O 5 The content of (A) is less than 10%, so that the glass cost is reduced, the crystallization upper limit temperature of the glass can be effectively reduced, the glass can be stably produced, and the desired optical constant is achieved. Therefore, the present invention 2 5 TaOThe content of (B) is 0 to 10%, preferably 5 to 10%.
Alkaline earth metal oxides such as BaO, caO, srO and MgO can lower the chemical stability of the glass and raise the crystallization upper limit temperature, but if the respective contents thereof exceed 10%, the devitrification resistance of the glass is lowered, so that BaO in the present invention is 0 to 10%; the CaO content is 0 to 10 percent; the SrO content is 0-10%, and the MgO content is 0-10%.
Li 2 O、Na 2 O and K 2 O is a component for suppressing phase separation and improving the stability of the glass. When the content thereof exceeds 10%, there is a tendency that chemical stability is remarkably lowered or refractive index is lowered, and preferably, li 2 O、Na 2 O and K 2 The total amount of O is 0 to 10 percent.
According to an exemplary embodiment of the present invention, an optical glass is provided. The optical glass comprises the following components in percentage by mass relative to the total mass of the glass with the composition converted by oxides: b is 2 O 3 ：5～25％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0～10％，Ta 2 O 5 :0 to 10% and La in a total amount of 50 to 75% 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 ，La 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625.
By applying the technical scheme of the invention, the components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass has excellent devitrification resistance and optical performance, and is easy to realize mass production.
According to a typical embodiment of the present invention, the optical glass further comprises a material selected from the group consisting of ZnO, baO, caO, srO, WO 3 、Sb 2 O 3 、Li 2 O、Na 2 O and K 2 O, and the contents are as follows: znO:0 to 15%, baO:0 to 10 percent; caO:0 to 10 percent; srO:0 to 10 percent; WO 3 ：0～10％；Sb 2 O 3 ：0～1％，Li 2 O、Na 2 O and K 2 The total amount of O is 0 to 10 percent.
According to a typical embodiment of the present invention, the optical glass consists of B in mass percent relative to the total mass of the glass of the composition in terms of oxides 2 O 3 ：5～25％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0～10％，ZnO：0～15％，BaO：0～10％，CaO：0～10％，SrO：0～10％，MgO：0～10％，WO 3 ：0～10％，Ta 2 O 5 :0 to 10 percent of Li and the total amount of Li is 0 to 10 percent 2 O、Na 2 O and K 2 O，Sb 2 O 3 :0 to 1% and La in a total amount of 50 to 75% 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 Composition of, wherein, la 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625. The components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass has better devitrification resistance and excellent optical performance, and is easy for mass production.
Preferably, according to an exemplary embodiment of the present invention, the optical component is contained in percentage by mass with respect to the total mass of the glass of the composition converted by oxidesThe glass comprises: b is 2 O 3 ：8～22％，Nb 2 O 5 ：5.6～10％，SiO 2 ：3～10％，ZrO 2 ：3～12％，TiO 2 ：0.5～7％，Ta 2 O 5 :5 to 10% and La in a total amount of 55 to 70% 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 ，La 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625.
In the present invention, Y 2 O 3 The melting property and devitrification resistance of the glass can be improved and the upper limit temperature of devitrification of the glass can be lowered, but if the content exceeds a certain amount, the stability and devitrification resistance of the glass are lowered. WO 3 Acts to increase the refractive index, but when WO is used 3 When the content exceeds 10%, the devitrification tendency tends to be strong, vitrification tends to be difficult, the dispersion is remarkably improved, and the transmittance on the short wavelength side of the visible light region of the glass is lowered and the coloring tendency tends to be increased, so that WO is preferable in the present invention 3 The content of (A) is 0-10%. According to an exemplary embodiment of the present invention, the optical glass preferably does not contain Y 2 O 3 And/or WO 3 。
In the present invention by controlling Nb 2 O 5 Content of (D) and SiO 2 Ratio of contents of Nb 2 O 5 /SiO 2 Within 0.75-2, the glass has the advantages of increased melting property, effectively increased glass stability, less striae, good glass uniformity, improved refractive index, crystallization resistance and chemical durability, especially Nb 2 O 5 /SiO 2 The effect is especially obvious when the ratio is 1-1.5.
By adding small amounts of Sb 2 O 3 、SnO 2 、CeO 2 The component can improve the fining effect of the glass, but when Sb is used 2 O 3 When the content exceeds 1%, the glass tends to have a lowered fining property and the deterioration of the forming mold is promoted by its strong oxidizing action, so thatPreferred Sb in the invention 2 O 3 The amount of (B) is 0 to 1%, more preferably 0 to 0.5%. SnO 2 However, when the content exceeds 1%, the glass is colored, or when the glass is heated, softened, press-molded or the like and then re-molded, sn becomes a starting point of crystal nucleus generation, and thus, devitrification tends to occur. Thus the SnO of the invention 2 The content of (b) is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not added. CeO (CeO) 2 Action and addition amount ratio of (B) and SnO 2 The content is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably no addition.
A certain amount of P can be properly introduced without affecting the performance of the optical glass of the present invention 2 O 5 、Al 2 O 3 、Bi 2 O 3 、GeO 2 、Lu 2 O 3 And F and the like.
The optical glass of the present invention is a high refractive index low dispersion glass, and a lens made of the high refractive index low dispersion glass is often used in combination with a lens made of the high refractive index high dispersion glass for chromatic aberration correction, and when the optical glass is used as a lens, the lens can be thinned as the refractive index is increased, and it is advantageous for miniaturization of optical devices that the refractive index nd of the optical glass of the present invention is > 1.87, preferably nd > 1.88, and the Abbe number vd > 38.0, preferably vd > 39.0.
The ability of the polished surface of the optical glass element to resist the action of various erosion media such as water, acid and the like during the manufacturing and use process is called the chemical stability of the optical glass, which mainly depends on the chemical components of the glass, and the stability Dw (powder method) of the optical glass of the invention to water action is above grade 3, preferably above grade 2, and more preferably above grade 1; stability against acid action D A The (powder method) is grade 3 or more, preferably grade 2 or more, and more preferably grade 1.
Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a 180 x 10mm sample, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass. The lower the crystallization upper limit temperature of the glass is, the stronger the stability of the glass at high temperature is, and the better the production process performance is. According to an exemplary embodiment of the present invention, the upper crystallization temperature of the optical glass is preferably below 1350 ℃, preferably below 1300 ℃, more preferably below 1280 ℃. The degree of streaking is a ratio of 4, i.e., A, B, C, D, in which A is a ratio of fine and scattered streaks under a predetermined detection condition, B is a ratio of fine and scattered streaks under a predetermined detection condition, C is a ratio of fine and parallel streaks under a predetermined detection condition, and D is a ratio of coarse streaks under a predetermined detection condition, as compared with a standard sample, from a direction in which streaks are most easily seen by using a streaking instrument composed of a point light source and a lens.
The bubble quality of the optical glass is measured according to the test method specified in GB/T7962.8-2010. The bubble degree is the grade of the allowable bubble content in the glass, the bubbles not only influence the appearance quality of a glass product, but also influence the optical performance, transparency, mechanical strength and the like of the glass, and cause a plurality of adverse effects on the glass, so the control of the bubble degree of the glass is very important, and the invention controls the bubble degree of the rare earth oxide La by controlling 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total content of (A) can further achieve a glass bubble degree of class A or more, preferably class A 0 More than class A, more preferably A 00 And (4) stages.
According to another aspect of the present invention, there is provided a glass preform or an optical element. The glass preform or the optical element is produced from any of the above optical glasses. The optical prefabricated member of the invention has the characteristics of high refractive index and low dispersion; the optical element of the present invention has high refractive index and low dispersion characteristics, and can provide optical elements such as various lenses and prisms having excellent optical performance. Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface. This lens is suitable as a lens for chromatic aberration correction, which can correct chromatic aberration by combining with a lens made of high-refractive-index, high-dispersion glass. Further, the lens is also effective for the compactness of an optical system. Further, since the prism has a high refractive index, by combining the prism with an imaging optical system and bending the optical path to direct the prism in a desired direction, a compact and wide-angle optical system can be realized.
According to a further aspect of the present invention, there is provided an optical instrument including an optical element, the optical element being any one of the optical elements described above. The optical instrument of the present invention may be a digital camera, a video camera, or the like.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Examples
Examples of optical glasses
In order to obtain glasses having compositions shown in tables 1 to 6, carbonates, nitrates, hydroxides, oxides, boric acid, etc. were used as raw materials, raw materials corresponding to optical glass components were weighed in proportion, mixed thoroughly to obtain a blended raw material, the blended raw material was put into a platinum crucible, heated to 1200 to 1450 ℃, melted, stirred, and clarified to form a uniform molten glass, and the molten glass was appropriately cooled, poured into a preheated mold, kept at 650 to 700 ℃ for 2 to 4 hours, and then slowly cooled to obtain optical glass. The characteristics of each glass were measured by the following methods, and the measurement results are shown in tables 1 to 6.
(1) Upper limit temperature of crystallization
Measuring the crystallization performance of the glass by adopting a temperature gradient furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.
(2) Refractive index nd and Abbe number vd
The refractive index and the Abbe number were measured according to the method specified in GB/T7962.1-2010.
(3) Chemical stability
Testing the stability Dw to Water and D to acid according to GB/T17129 A . Increase chemical stability
(4) Degree of striae
The measurement was carried out in accordance with the method defined in MLL-G-174B.
(5) Degree of bubbling
The bubble quality of the optical glass is measured according to the test method specified in GB/T7962.8-2010.
TABLE 1
Figure BDA0001769585250000071
Figure BDA0001769585250000081
TABLE 2
The components are% Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14
B 2 O 3 5.9 9 8 6.9 9.6 10.9 16
Nb 2 O 5 7.4 6.5 6.5 7.3 7.4 6.7 6.7
SiO 2 5.8 4 4 4.5 3.8 5.8 5.9
ZrO 2 6 3 2.8 4 6 5.8 5.8
TiO 2 0.9 2.4 2.6 1.5 2.8 3 1.5
La 2 O 3 36 25 25.8 27.8 32 33.5 34
Gd 2 O 3 21.4 15.9 15.9 16.8 25.4 26 26
Y 2 O 3 0 10 10 0 0 0 1
Yb 2 O 3 0 0 0 8 0 0 0.5
Ta 2 O 5 10 3.4 3.6 6 6.4 5.7 0
ZnO 0 15 15 0 0 0 0
BaO 0 0 3 8 0 0 0
CaO 2 2 0 0 2 2.6 2.6
SrO 0 3 2.3 0 0 0 0
MgO 0 0 0 0 0 0 0
WO 3 0 0 0 0 0 0 0
Sb 2 O 3 0 0.8 0.5 0 0 0 0
Li 2 O 3.5 0 0 4.5 3.5 0 0
Na 2 O 1.1 0 0 4.7 1.1 0 0
K 2 O 0 0 0 0 0 0 0
La 2 O 3 /Gd 2 O 3 1.682243 1.572327 1.622642 1.654762 1.259843 1.288462 1.307692
La 2 O 3 +Gd 2 O 3 +Y 2 O 3 +Yb 2 O 3 57.4 50.9 51.7 52.6 57.4 59.5 61.5
Nb 2 O 5 /SiO 2 1.275862 1.625 1.625 1.622222 1.947368 1.155172 1.135593
Li 2 O+Na 2 O+K 2 O 4.6 0 0 9.2 4.6 0 0
Total amount of 100 100 100 100 100 100 100
Upper limit temperature of crystallization 1300 1300 1340 1360 1370 1330 1290
Refractive index nd 1.877 1.875 1.874 1.875 1.881 1.885 1.883
Abbe number vd 38.25 38.77 38.82 38.95 38.79 39.22 39.21
Stability to Water action D w 2 2 2 3 3 1 1
Stability against acid action D A 2 2 2 3 3 1 1
Stripe A C C C C A A
Degree of bubbling A A 0 A 0 A A A A 00
TABLE 3
The components are% Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21
B 2 O 3 14 10.5 6.4 6.8 7.5 5.7 5
Nb 2 O 5 5.6 6 4.2 2.5 10 13 15
SiO 2 6 5.8 6.1 1.3 6.2 4.4 3.1
ZrO 2 6 6.1 6.2 7.5 5.9 5.8 3.8
TiO 2 2.2 1.9 0.8 0.5 4 7 10
La 2 O 3 38.2 38.5 38.8 39 37 34 30
Gd 2 O 3 25.4 24 26 27.8 25.8 26 26
Y 2 O 3 0 0 5.5 0 0 0 0
Yb 2 O 3 0 0 0 0 0 0 0
Ta 2 O 5 0 3.6 6 3.4 3.6 4.1 5
ZnO 0 0 0 11.2 0 0 0
BaO 0 1.3 0 0 0 0 0
CaO 0 0 0 0 0 0 0
SrO 0 2.3 0 0 0 0 0
MgO 0 0 0 0 0 0 0
WO 3 2.6 0 0 0 0 0 0
Sb 2 O 3 0 0 0 0 0 0 0
Li 2 O 0 0 0 0 0 0 0
Na 2 O 0 0 0 0 0 0 0
K 2 O 0 0 0 0 0 0 2.1
La 2 O 3 /Gd 2 O 3 1.503937 1.604167 1.492308 1.402878 1.434109 1.307692 1.153846
La 2 O 3 +Gd 2 O 3 +Y 2 O 3 +Yb 2 O 3 63.6 62.5 70.3 66.8 62.8 60 56
Nb 2 O 5 /SiO 2 0.933333 1.034483 0.688525 1.923077 1.612903 2.954545 4.83871
Li 2 O+Na 2 O+K 2 O 0 0 0 0 0 0 2.1
Total amount of 100 100 100 100 100 100 100
Upper limit temperature of crystallization 1280 1300 1290 1285 1285 1300 1320
Refractive index nd 1.885 1.875 1.889 1.885 1.883 1.885 1.879
Abbe number vd 38.8 39.12 39.13 39.21 39.31 39.01 39.25
Stability to Water action D w 1 1 1 2 2 2 2
Stability against acid action D A 1 1 1 2 2 2 2
Stripe C A D C C D D
Degree of bubbling A A 0 A 00 A 00 A 00 A 0 A
TABLE 4
Figure BDA0001769585250000091
Figure BDA0001769585250000101
TABLE 5
Figure BDA0001769585250000102
Figure BDA0001769585250000111
TABLE 6
Figure BDA0001769585250000112
Figure BDA0001769585250000121
Optical preform embodiments
The optical glass obtained in example 1 in table 1 was cut into a predetermined size, and a mold release agent made of boron nitride powder was uniformly applied on the surface, and then heated, softened, and pressure-molded to produce preforms of various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens.
Optical element embodiments
The preforms obtained in the above examples of optical preforms were annealed to reduce the deformation inside the glass and to fine-tune the optical properties such as refractive index to the desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be further coated with an antireflection film.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (19)

1. An optical glass comprising, in mass percent, with respect to the total mass of the glass of a composition converted to oxides: B2O3:5 to 25%, nb2O5:2 to 15%, siO2:0.5 to 15%, zrO2:1 to 15%, tiO2:0 to 10%, ta2O5:0 to 10 percent of La2O3, gd2O3, Y2O3 and Yb2O3, wherein the total amount of the La2O3 and the Gd2O3 is 50 to 75 percent, and the weight ratio of the La2O3 to the Gd2O3 is 1.3 to 1.6; the weight ratio Nb2O5/SiO2 of Nb2O5 to SiO2 is 0.75 to 1.266667, and the stripes of the optical glass are above grade C.
2. An optical glass according to claim 1, wherein the optical glass further comprises a material selected from the group consisting of ZnO, baO, caO, srO, mgO, WO 3 、Sb 2 O 3 、Li 2 O、Na 2 O and K 2 O, and the content is as follows: znO:0 to 15%, baO:0 to 10%, caO:0 to 10%, srO:0 to 10%, mgO:0 to 10% by weight, WO 3 ：0~10%，Sb 2 O 3 ：0~1%，Li 2 O、Na 2 O and K 2 The total amount of O is 0 to 10%.
3. The optical glass according to claim 1, wherein the optical glass consists of B in percent by mass relative to the total mass of the glass in terms of oxide of the composition 2 O 3 ：5~25%，Nb 2 O 5 ：2~15%，SiO 2 ：0.5~15%，ZrO 2 ：1~15%，TiO 2 ：0~10%，ZnO：0~15%，BaO：0~10%，CaO：0~10%，SrO：0~10%，MgO：0~10%，WO 3 ：0~10%，Ta 2 O 5 :0 to 10 percent of Li, and the total amount is 0 to 10 percent 2 O、Na 2 O and K 2 O，Sb 2 O 3 :0~1% and 50 to 75% of La in total 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 Composition of, wherein, la 2 O 3 With Gd 2 O 3 La by weight of 2 O 3 /Gd 2 O 3 The range is 1.3 to 1.6.
4. The optical glass according to claim 1 or 3, wherein the optical glass comprises, in mass percent, with respect to the total mass of the glass of the composition as converted to oxides: b is 2 O 3 ：8~22%，Nb 2 O 5 ：5.6~10%，SiO 2 ：3~10%，ZrO 2 ：3~12%，TiO 2 ：0.5~7%，Ta 2 O 5 :5 to 10% and/or 55 to 70% of La in total 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 。
5. The optical glass according to claim 1, wherein La 2 O 3 /Gd 2 O 3 1.4 to 1.5.
6. The optical glass according to claim 1 or 2, wherein the optical glass does not contain Y 2 O 3 And/or WO 3 。
7. Optical glass according to any of claims 1 to 3, characterised in that Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 0.75 to 1.157895.
8. The optical glass according to any one of claims 1 to 3, wherein the optical glass has a crystallization upper limit temperature of less than 1350 ℃.
9. The optical glass according to claim 8, wherein the optical glass has a crystallization upper limit temperature of less than 1300 ℃.
10. An optical glass according to any one of claims 1 to 3, characterised in that the refractive index nd of the optical glass is > 1.87; the Abbe number vd is more than 38.0.
11. An optical glass according to claim 10, characterised in that the refractive index nd of the optical glass is > 1.88; the Abbe number vd is more than 39.0.
12. An optical glass according to any one of claims 1 to 3, wherein the water-resistance stability Dw of the optical glass is above grade 3; stability against acid action D A Above level 3.
13. The optical glass according to claim 12, wherein the stability Dw against water effect of the optical glass is above grade 2; stability against acid action D A Above level 2.
14. The optical glass according to claim 13, whereinCharacterized in that the water-resistant stability Dw of the optical glass is 1 grade; stability against acid action D A At level 1.
15. The optical glass according to any one of claims 1 to 3, wherein the degree of blistering is class A or higher.
16. The optical glass according to claim 15, wherein the striae of the optical glass are of class B or higher; degree of bubbling of A 0 More than grade.
17. The optical glass according to claim 16, wherein the optical glass has a streak of class a; degree of bubbling A 00 And (4) stage.
18. A glass preform or optical element produced from the optical glass of any one of claims 1 to 17.
19. An optical instrument comprising an optical element, wherein the optical element is the optical element of claim 18.
CN201810943256.4A 2018-08-17 2018-08-17 Optical glass, glass preform or optical element prepared from optical glass, and optical instrument Active CN110835232B (en)

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