CN117756402A - Optical glass and optical element - Google Patents

Optical glass and optical element Download PDF

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Publication number
CN117756402A
CN117756402A CN202311805778.5A CN202311805778A CN117756402A CN 117756402 A CN117756402 A CN 117756402A CN 202311805778 A CN202311805778 A CN 202311805778A CN 117756402 A CN117756402 A CN 117756402A
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sio
less
tio
glass
optical glass
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匡波
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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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 ：12～35％；Nb 2 O 5 +TiO 2 +WO 3 ：25～55％；BaO+SrO+CaO+MgO：16～50％；ZnO：0～10％；Ln 2 O 3 ：0～10％；ZrO 2 :0 to 10 percent, wherein B 2 O 3 /SiO 2 Is 0.4 or less, (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.5 to 2.2, (ZnO+SrO+Ln) 2 O 3 )/SiO 2 The refractive index of the optical glass is not more than 0.7, and the Abbe number is not more than 30. Through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number, and simultaneously has excellent chemical stability and lower density, thereby meeting the use of high-performance optical instruments.

Description

Optical glass and optical element
The present application is a divisional application of the invention patent application named "optical glass and optical element" for 202111042942.2, 2021, 09, 07.
Technical Field
The present invention relates to an optical glass, and more particularly, to an optical glass having a refractive index of 1.88 or more and an abbe number of 30 or less, and an optical element made of the same.
Background
The optical glass with the refractive index of more than 1.88 and the Abbe number of less than 30 belongs to high-refraction high-dispersion optical glass, the glass can be coupled with low-dispersion optical glass for use, chromatic aberration and secondary spectrum can be effectively eliminated, meanwhile, the total optical length of a lens can be effectively shortened, and an imaging system is miniaturized, so that the glass has wide application prospect in optical design.
In recent years, with the progress of digitization and higher definition of instruments using optical systems, there is an increasing demand for weight reduction of optical elements such as lenses used in various optical instruments, which requires optical glasses for manufacturing optical elements to have a lower density. On the other hand, the optical glass is inevitably eroded by the environment and various liquids (such as acid, alkali, water and the like) during processing and use, so that the resistance of the optical glass to the erosion, namely the chemical stability of the optical glass is important to the use precision and the service life of the optical instrument.
Disclosure of Invention
For the above reasons, the technical problem to be solved by the invention is to provide the optical glass with excellent chemical stability and lower density.
The technical scheme adopted for solving the technical problems is as follows:
the optical glass comprises the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 ：12～35％；Nb 2 O 5 +TiO 2 +WO 3 ：20～55％；BaO+SrO+CaO+MgO：16～55％；ZnO：0～10％；Ln 2 O 3 ：0～10％；ZrO 2 :0 to 10 percent, wherein B 2 O 3 /SiO 2 Is 0.4 or less, (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.5 to 2.2, (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.7 or less, ln is 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the above, the refractive index n of the optical glass d An Abbe number v of 1.88 or more d Is 30 or less.
Further, the optical glass comprises the following components in percentage by weight, Also contains: r is R 2 O: 0-10%; and/or Al 2 O 3 : 0-5%; and/or clarifying agent: 0 to 1 percent, wherein R is 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more of the following.
Further, the optical glass comprises the following components in percentage by weight: nb (Nb) 2 O 5 BaO is 0.2 to 1.2, preferably Nb 2 O 5 BaO is 0.2 to 1.0, more preferably Nb 2 O 5 BaO is 0.25 to 0.9, nb is more preferable 2 O 5 BaO is 0.3-0.8; and/or TiO 2 /(Nb 2 O 5 +ZrO 2 ) From 0.6 to 5.5, preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) From 0.7 to 4.0, more preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) From 0.8 to 3.0, tiO being further preferred 2 /(Nb 2 O 5 +ZrO 2 ) 1.0 to 2.5; and/or SiO 2 /(Nb 2 O 5 +TiO 2 ) From 0.3 to 1.3, preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) From 0.35 to 1.0, more preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.4 to 0.8.
Further, the optical glass comprises the following components in percentage by weight: b (B) 2 O 3 /SiO 2 From 0.01 to 0.3, preferably B 2 O 3 /SiO 2 0.03 to 0.2; and/or (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.6 or less, preferably (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.5 or less, more preferably (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.3 or less; and/or (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.6 to 2.0, preferably (SiO) 2 +TiO 2 )/
(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.8 to 1.8, more preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is 0.9 to 1.5.
Further, the optical glass comprises the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 :15 to 30%, preferably SiO 2 +B 2 O 3 : 18-25%; and/or Nb 2 O 5 +TiO 2 +WO 3 :25 to 50%, preferably Nb 2 O 5 +TiO 2 +WO 3 : 30-45%; and/or bao+sro+cao+mgo:20 to 50%, preferably BaO+SrO+CaO+MgO: 25-40%; and/or ZnO:0 to 5%, preferably ZnO:0 to 2 percent; and/or Ln 2 O 3 :0 to 9%, preferably Ln 2 O 3 : 0-7%; and/or ZrO 2 :1 to 8%, preferably ZrO 2 : 2-7%; and/or R 2 O:0 to 6%, preferably R 2 O:0.5 to 5 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of R 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more of the following.
Further, the optical glass comprises the following components in percentage by weight: siO (SiO) 2 :12 to 30%, preferably SiO 2 :15 to 25%, more preferably SiO 2 : 16-23%; and/or Nb 2 O 5 :6 to 20%, preferably Nb 2 O 5 :7 to 18%, more preferably Nb 2 O 5 : 8-17%; and/or TiO 2 :15 to 35%, preferably TiO 2 :18 to 32%, more preferably TiO 2 : 20-30%; and/or BaO: 15-35%, preferably BaO:18 to 32%, more preferably BaO: 20-30%; and/or CaO:0 to 12%, preferably CaO:1 to 9%, more preferably CaO: 3-7%; and/or B 2 O 3 :0 to 6%, preferably B 2 O 3 :0.1 to 5%, more preferably B 2 O 3 :0.5 to 4 percent; and/or WO 3 :0 to 10%, preferably WO 3 : from 0 to 5%, more preferably WO 3 :0 to 2 percent; and/or SrO: 0-8%, preferably SrO:0 to 4%, more preferably SrO:0 to 2 percent; and/or MgO:0 to 8%, preferably MgO:0 to 4%, more preferably MgO:0 to 2 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 2%, more preferably Li 2 O:0 to 1 percent; and/or Na 2 O:0 to 8%, preferably Na 2 O:0 to 6%, more preferably Na 2 O:0.5 to 5 percent; and/or K 2 O:0 to 5%, preferably K 2 O:0 to 3%, more preferably K 2 O：0～2％。
Further, the optical glass comprises the following components in percentage by weight: na (Na) 2 O/CaO is 5.0 or less, preferably Na 2 O/CaO is 0.01 to 3.0, more preferably Na 2 0.05 to 2.5 percent of O/CaO; and/or Li 2 O/B 2 O 3 Is 0.5 or less, preferably Li 2 O/B 2 O 3 Is 0.3 or less, more preferably Li 2 O/B 2 O 3 Is 0.1 or less, more preferably Li 2 O/B 2 O 3 Is 0.05 or less; and/or 10 xLi 2 O/Nb 2 O 5 Is 0.7 or less, preferably 10 xLi 2 O/Nb 2 O 5 Is 0.4 or less, more preferably 10×Li 2 O/Nb 2 O 5 Is 0.2 or less.
Further, the optical glass comprises the following components in percentage by weight: not more than 4% of P 2 O 5 Preferably not more than 2% P 2 O 5 More preferably, not more than 1% P 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% Bi 2 O 3 Preferably not more than 2% Bi 2 O 3 More preferably not more than 1% Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% Ta 2 O 5 Preferably not more than 2% Ta 2 O 5 More preferably not more than 1% Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% TeO 2 Preferably not more than 2% TeO 2 More preferably notTeO exceeding 1% 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% Ga 2 O 3 Preferably not more than 2% Ga 2 O 3 More preferably not more than 1% Ga 2 O 3 。
Furthermore, the optical glass does not contain ZnO; and/or does not contain Li 2 O; and/or does not contain SrO; and/or does not contain MgO; and/or does not contain P 2 0 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Gd 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Y 2 O 3 。
Further, the refractive index n of the optical glass d 1.89 to 1.95, preferably 1.90 to 1.94, more preferably 1.91 to 1.935; abbe number v d 20 to 27, more preferably 21 to 26, and still more preferably 22 to 25.
Further, lambda of the optical glass 70 Is 460nm or less, preferably lambda 70 Is 450nm or less, more preferably lambda 70 440nm or less; and/or lambda 5 Is 400nm or less, preferably lambda 5 Is 390nm or less, more preferably lambda 5 380nm or less; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or stability against water action D W More than 2 types, preferably 1 type; and/or the upper crystallization limit temperature is 1180 ℃ or lower, preferably 1160 ℃ or lower, more preferably 1140 ℃ or lower; and/or Young's modulus E of 9500×10 7 Preferably 10000X 10 or more per Pa 7 Preferably 10500×10 or more per Pa 7 The pressure of the mixture is higher than/Pa; and/or coefficient of thermal expansion alpha 100～300℃ 110X 10 -7 Preferably 105X 10, K or less -7 Preferably less than or equal to K, more preferably 100X 10 -7 and/K or below; density ρ of 4.30g/cm 3 Hereinafter, it is preferably 4.20g/cm 3 Hereinafter, it is more preferably 4.10g/cm 3 The following are set forth; and/or abrasion degree F A 150 or more, preferably 180 or more, more preferably 200 to 300; and/or relative partial dispersion P g,F From 0.6000 to 0.6400, preferably from 0.6100 to 0.6300, more preferablyPreferably 0.6150 to 0.6250.
And a glass preform made of the optical glass.
The optical element is made of the optical glass or the glass prefabricated member.
An optical device comprising the above optical glass or the above optical element.
The beneficial effects of the invention are as follows: through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number, and simultaneously has excellent chemical stability and lower density, thereby meeting the use of high-performance optical instruments.
Detailed Description
The embodiments of the optical glass of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the repeated explanation, the explanation is omitted appropriately, but the gist of the present invention is not limited thereto. In the following, the optical glass of the present invention may be simply referred to as glass.
[ optical glass ]
The respective component ranges of the optical glass of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of weight percent (wt%) with respect to the total amount of glass substance converted into the composition of oxide. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the optical glass composition of the present invention is 100% when the oxide, the composite salt, the hydroxide, and the like are melted and decomposed and converted into oxide.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "about" as used herein means that the formulations, parameters and other quantities and characteristics are not, and need not be, exact, and may be approximated and/or greater or lesser, if desired, reflecting tolerances, conversion factors, measurement errors and the like. The term "and/or" as used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.
< essential component and unnecessary component >
SiO 2 And B 2 O 3 The glass skeleton is a component that can improve the stability of the glass, and when the total content of the components is high, it is difficult to obtain the desired high refractive index of the present invention. Thus, siO 2 And B 2 O 3 Is the total content of SiO 2 +B 2 O 3 From 12 to 35%, preferably SiO 2 +B 2 O 3 15 to 30%, more preferably SiO 2 +B 2 O 3 18 to 25 percent. In some embodiments, siO 2 +B 2 O 3 Is about 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%.
SiO 2 The glass network generator has the functions of maintaining the chemical stability of glass and the viscosity suitable for forming molten glass, improving the devitrification resistance of glass and reducing the erosion of molten glass liquid to refractory materials. If SiO is 2 The content is less than 12%, and it is difficult to achieve the above effect, so SiO 2 The lower limit of the content of (2) is 12%, preferably 15%, more preferably 16%. If SiO is 2 If the content of (2) is more than 30%, the glass-melting property is lowered and the transition temperature is increased. Thus, siO 2 The upper limit of the content of (2) is 30%, preferably 25%, more preferably 23%. In some embodiments, about 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17% may be included17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30% SiO 2 。
B 2 O 3 Can improve the thermal stability of the glass, improve the meltability of the glass, inhibit the rapid escape of gas when the raw materials are melted so as to avoid 'out-of-jar', and when the glass is properly contained, the glass without glass raw materials melting residues can be easily obtained, but when B 2 O 3 When the content of (B) is too large, the refractive index of the glass is lowered and the thermal stability is deteriorated, so that B in the present invention 2 O 3 The content of (2) is 6% or less, preferably 0.1 to 5%, more preferably 0.5 to 4%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% B may be included 2 O 3 。
In some embodiments of the invention, B 2 O 3 Content of (2) and SiO 2 Ratio B between the contents of (2) 2 O 3 /SiO 2 The control of the temperature below 0.4 is beneficial to improving the chemical stability of the glass. Therefore, B is preferred 2 O 3 /SiO 2 Is 0.4 or less. Further, by making B 2 O 3 /SiO 2 In the range of 0.01 to 0.3, the Young's modulus and the abrasion degree of the glass are also beneficial to optimization. Therefore, B is more preferable 2 O 3 /SiO 2 From 0.01 to 0.3, further preferably B 2 O 3 /SiO 2 0.03 to 0.2. In some embodiments, B 2 O 3 /SiO 2 The values of (2) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24,0.25、0.26、0.27、0.28、0.29、0.3、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.4。
Nb 2 O 5 、TiO 2 、WO 3 Is a high-refraction high-dispersion component, when the total content of Nb 2 O 5 +TiO 2 +WO 3 When the value of (2) is less than 20%, the refractive index and dispersion of the glass hardly meet the design requirements; when it is added up to Nb 2 O 5 +TiO 2 +WO 3 When the value of (2) is more than 55%, the devitrification resistance and chemical stability of the glass are lowered, and the light transmittance is deteriorated. Thus, nb in the present invention 2 O 5 +TiO 2 +WO 3 20 to 55%, preferably Nb 2 O 5 +TiO 2 +WO 3 From 25 to 50%, more preferably Nb 2 O 5 +TiO 2 +WO 3 30 to 45 percent. In some embodiments, nb 2 O 5 +TiO 2 +WO 3 Is about 20%, 20.5%, 21%, 21.5%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53.5%, 54%, 54.5%, 55%.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index and devitrification resistance of the glass and reduce the thermal expansion coefficient of the glass, and contains more than 6 percent of Nb 2 O 5 To obtain the above effect, nb is preferable 2 O 5 The content of (2) is 7% or more, more preferably 8% or more. If Nb is 2 O 5 The content of (2) exceeds 20%, and the thermal stability and chemical stability of the glass are lowered, and the light transmittance is lowered, so that Nb in the present invention 2 O 5 The upper limit of the content of (2) is 20%, preferably 18%, more preferably 17%. In some embodiments, about 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20% Nb may be included 2 O 5 。
TiO 2 The glass has the functions of improving the refractive index and dispersion of the glass, can participate in the formation of a glass network, and can be more stable and reduce the high-temperature viscosity of the glass by proper amount. In the invention, the catalyst contains more than 15% of TiO 2 To obtain the above effect, it preferably contains 18% or more of TiO 2 More preferably, the composition contains at least 20% of TiO 2 . If TiO 2 When the content exceeds 35%, the crystallization tendency of the glass increases, the transition temperature increases, and the glass becomes easily colored during press molding. Thus, in the present invention, tiO 2 The content of (2) is less than 35%, preferably TiO 2 The content of (2) is 32% or less, more preferably 30% or less. In some embodiments of the invention, about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35% TiO may be included 2 。
In some embodiments of the invention, by combining SiO 2 Content of (2) and Nb 2 O 5 And TiO 2 Is the sum of Nb 2 O 5 +TiO 2 Ratio between SiO 2 /(Nb 2 O 5 +TiO 2 ) The glass can obtain proper abrasion degree and relative partial dispersion while reducing the thermal expansion coefficient and density of the glass by controlling the glass within the range of 0.3-1.3. Therefore, siO is preferred 2 /(Nb 2 O 5 +TiO 2 ) From 0.3 to 1.3, more preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) From 0.35 to 1.0, siO is more preferable 2 /(Nb 2 O 5 +TiO 2 ) 0.4 to 0.8. In some embodiments of the invention, siO 2 /(Nb 2 O 5 +TiO 2 ) The values of (2) may be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3.
WO 3 Can improve the refractive index and dispersion of the glass, but has the effect less than Nb 2 O 5 And TiO 2 Without the cost advantage and at the same time, the light transmittance of the glass is reduced. Thus, in the present invention WO 3 The content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and even more preferably no WO is contained 3 . In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% of WO may be included 3 。
ZnO can adjust the refractive index and dispersion of the glass, reduce the transition temperature of the glass, if the content exceeds 10%, the crystallization resistance of the glass is reduced, meanwhile, the high-temperature viscosity is smaller, the difficulty is brought to molding, and the thermal expansion coefficient and the refractive index temperature coefficient of the glass are increased. Accordingly, the ZnO content in the present invention is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%. In some embodiments, it is further preferred that ZnO is absent. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% ZnO may be included.
R 2 O(R 2 O is Li 2 O、Na 2 O、K 2 One or more of O) can lower the glass transition temperature, and when the content exceeds 10%, the glassThe chemical stability of (c) is reduced. Thus, R is 2 The content of O is 0 to 10%, preferably 0 to 6%, more preferably 0.5 to 5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% of R may be included 2 O。
Li 2 O can lower the glass transition temperature and improve the glass meltability, but at high content, it is detrimental to the chemical stability, crystallization resistance and thermal expansion coefficient of the glass, and therefore Li in the present invention 2 The content of O is 3% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred that Li is not contained 2 O. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% Li may be included 2 O。
In some embodiments of the invention, by causing Li to be 2 O content and B 2 O 3 Ratio between the contents of Li 2 O/B 2 O 3 The chemical stability and the secondary compression type surface crystallization resistance of the glass can be improved below 0.5, and the abrasion degree of the glass is optimized. Therefore, li is preferred 2 O/B 2 O 3 Is 0.5 or less, more preferably Li 2 O/B 2 O 3 Is 0.3 or less, more preferably Li 2 O/B 2 O 3 Is 0.1 or less, more preferably Li 2 O/B 2 O 3 Is 0.05 or less. In some embodiments, li 2 O/B 2 O 3 The value of (2) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24、0.25、0.26、0.27、0.28、0.29、0.3、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.4、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.5。
In some embodiments of the invention, the method is carried out by subjecting 10×Li 2 O/Nb 2 O 5 The glass has the chemical stability and the secondary compression crystallization resistance of being beneficial to improving the Young modulus of the glass when the glass is below 0.7. Therefore, 10×Li is preferable 2 O/Nb 2 O 5 Is 0.7 or less, more preferably 10×Li 2 O/Nb 2 O 5 Is 0.4 or less, more preferably 10×Li 2 O/Nb 2 O 5 Is 0.2 or less. In some embodiments of the invention, 10×Li 2 O/Nb 2 O 5 The values of (c) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.55, 0.6, 0.65, 0.7.
Na 2 O has the function of improving glass melting property, can improve glass melting effect, can reduce the transition temperature of glass at the same time, in the invention, a proper amount of O can also improve the light transmittance of glass. If Na is 2 O content exceeding 8%, chemical stability and weather resistance of the glass are lowered, so Na 2 O content is 0-8%, preferably Na 2 O content is 0 to 6%, more preferably Na 2 The content of O is 0.5-5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Na may be included 2 O。
K 2 O has the effect of improving the thermal stability and meltability of the glass, but its content exceeds 5%, devitrification resistance and chemical resistance of the glassDeterioration of the chemical stability, therefore, K in the present invention 2 The content of O is less than 5%, preferably K 2 The content of O is 3% or less, more preferably 2% or less. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% K may be included 2 O。
The appropriate amounts of alkaline earth oxide BaO, srO, caO and MgO in the glass can adjust the refractive index and dispersion of the glass and can improve the stability of the glass, and the above effects can be obtained by containing 16% or more of alkaline earth oxide in the present invention. On the other hand, if the value of bao+sro+cao+mgo is more than 55%, the refractive index and dispersion of the glass hardly meet the design requirements, and the crystallization resistance of the glass is lowered. Therefore, in the present invention, baO+SrO+CaO+MgO is limited to 16 to 55%, preferably BaO+SrO+CaO+MgO is 20 to 50%, and more preferably BaO+SrO+CaO+MgO is 25 to 40%. In some embodiments, the bao+sro+cao+mgo content is about 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46.5%, 47%, 47.5%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 52.5%, 53%, 53.5%.
MgO can reduce the refractive index and melting temperature of the glass, but when the content of MgO is too high, the refractive index of the glass cannot meet the design requirement, the crystallization resistance and stability of the glass are reduced, and meanwhile, the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that MgO is not contained. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% MgO may be included.
CaO is helpful for adjusting the optical constant of the glass, improving the processing performance of the glass and reducing the density of the glass, but when the content of CaO is too large, the optical constant of the glass cannot meet the requirement, and the crystallization resistance is deteriorated. Therefore, the CaO content is limited to 0 to 12%, preferably 1 to 9%, more preferably 3 to 7%. In some embodiments, caO may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%.
In some embodiments of the invention, by controlling Na 2 Ratio Na between O content and CaO content 2 The O/CaO is below 5.0, and the crystallization resistance of the glass can be improved. Therefore, na is preferred 2 The O/CaO is less than 5.0. Further, by controlling Na 2 The O/CaO is in the range of 0.01 to 3.0, and is also beneficial to improving the light transmittance and Young modulus of the glass. Therefore, na is more preferable 2 O/CaO is 0.01 to 3.0, more preferably Na 2 The O/CaO is 0.05 to 2.5. In some embodiments of the invention, na 2 The O/CaO values may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4.5, 4.6, 4.7, 4.8, 4.9, 4.0.
SrO can adjust the refractive index and abbe number of the glass, but if the content is too large, the chemical stability of the glass is lowered, and the cost of the glass is also rapidly increased. Therefore, the SrO content is limited to 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that SrO is absent. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% SrO can be included.
BaO is an essential component for adjusting the refractive index of the glass and improving the transmittance and strength of the glass in the present invention, and the above effect is not remarkable when the content thereof is less than 15%, and the lower limit of the content of BaO is preferably 18%, more preferably 20%. On the other hand, if the content of BaO exceeds 35%, the crystallization resistance and chemical stability of the glass are deteriorated, and the density is remarkably increased. Therefore, the upper limit of the BaO content is 35%, preferably 32%, more preferably 30%. In some embodiments of the invention, about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35% BaO may be included.
In some embodiments of the invention, by controlling Nb 2 O 5 And the ratio Nb between BaO contents 2 O 5 BaO is in the range of 0.2 to 1.2, so that the glass has excellent chemical stability and simultaneously reduces the thermal expansion coefficient of the glass. Therefore, nb is preferable 2 O 5 BaO is 0.2 to 1.2, more preferably Nb 2 O 5 BaO is 0.2-1.0. Further, by controlling Nb 2 O 5 BaO is in the range of 0.25 to 0.9, and the Young's modulus of the glass can be further improved. Therefore, nb is more preferable 2 O 5 BaO is 0.25 to 0.9, nb being more preferred 2 O 5 BaO is 0.3 to 0.8. In some embodiments of the invention，Nb 2 O 5 The value of/BaO may be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2.
ZrO 2 Can improve the refractive index of the glass, adjust the dispersion, improve the crystallization resistance and the strength of the glass, if ZrO 2 The content of (2) is higher than 10%, the difficulty of glass melting is increased, the melting temperature is increased, and even inclusions and transmittance in the glass are reduced. Thus, zrO 2 The content is 10% or less, preferably 1 to 8%, more preferably 2 to 7%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% ZrO may be included 2 。
In some embodiments of the invention, by controlling the TiO 2 Content of (2) and Nb 2 O 5 And ZrO(s) 2 Is the sum of Nb 2 O 5 +ZrO 2 Ratio of TiO 2 /(Nb 2 O 5 +ZrO 2 ) Within the range of 0.6 to 5.5, the crystallization resistance and the light transmittance of the glass are improved. Therefore, tiO is preferred 2 /(Nb 2 O 5 +ZrO 2 ) From 0.6 to 5.5, more preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.7 to 4.0. Further, by controlling TiO 2 /(Nb 2 O 5 +ZrO 2 ) In the range of 0.8 to 3.0, proper abrasion and relative partial dispersion of the glass can be obtained. Therefore, tiO is further preferred 2 /(Nb 2 O 5 +ZrO 2 ) From 0.8 to 3.0, tiO being more preferred 2 /(Nb 2 O 5 +ZrO 2 ) 1.0 to 2.5. In some embodiments of the invention, the TiO 2 /(Nb 2 O 5 +ZrO 2 ) The value of (2) may be 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3.0、3.1、3.2、3.3、3.4、3.5、3.6、3.7、3.8、3.9、4.0、4.1、4.2、4.3、4.4、4.5、4.6、4.7、4.8、4.9、5.0、5.1、5.2、5.3、5.4、5.5。
In some embodiments of the invention, by combining SiO 2 And TiO 2 Is the total content of SiO 2 +TiO 2 With Nb 2 O 5 、ZrO 2 Total content of Nb, caO and BaO 2 O 5 +ZrO 2 The ratio between +CaO+BaO (SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is controlled within the range of 0.5-2.2, the glass forming stability and chemical stability of the glass can be improved, and the density of the glass can be reduced. Therefore, it is preferable that (SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.5 to 2.2, more preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is 0.6 to 2.0. Further, by controlling (SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is in the range of 0.8-1.8, and the secondary compression crystallization resistance and Young's modulus of the glass can be further improved. Therefore, it is more preferable that (SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is 0.8 to 1.8, more preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is 0.9 to 1.5. In some embodiments of the invention, (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +cao+bao) may be 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2.
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of these) are components that increase the refractive index and chemical stability of the glass,by combining Ln 2 O 3 The content of (2) is controlled to 10% or less, and the glass can be prevented from decreasing in devitrification resistance, preferably Ln 2 O 3 The upper limit of the content range is 9%, more preferably 7%. In some embodiments, ln is preferred 2 O 3 Is La (La) 2 O 3 . In some embodiments, it is preferred that Gd is absent 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Y 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or not containing Yb 2 O 3 . In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% Ln can be included 2 O 3 。
In some embodiments of the invention, the zinc oxide is prepared by combining ZnO, srO and Ln 2 O 3 In the total content of ZnO+SrO+Ln 2 O 3 With SiO 2 The ratio between the contents of (ZnO+SrO+Ln) 2 O 3 )/SiO 2 The control of the glass temperature below 0.7 is beneficial to reducing the density and relative partial dispersion of the glass. Therefore, (ZnO+SrO+Ln) is preferable 2 O 3 )/SiO 2 Is 0.7 or less, more preferably (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.6 or less. Further, by controlling (ZnO+SrO+Ln) 2 O 3 )/SiO 2 The thermal expansion coefficient of the glass can be reduced below 0.5. Therefore, (ZnO+SrO+Ln) is more preferable 2 O 3 )/SiO 2 Is 0.5 or less, more preferably (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.3 or less. In some embodiments of the invention, (ZnO+SrO+Ln) 2 O 3 )/SiO 2 The value of (c) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46,0.47、0.48、0.49、0.5、0.55、0.6、0.65、0.7。
Al 2 O 3 The chemical stability of the glass can be improved, but when the content is too large, the devitrification resistance and the meltability of the glass are reduced, so that the content is 5% or less, preferably 3% or less, more preferably 2% or less. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Al may be included 2 O 3 。
In some embodiments, the glass of the present invention may also contain 0-1% fining agent to enhance the bubble removal ability of the glass. Such fining agents include, but are not limited to, sb 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a), preferably Sb 2 O 3 As a clarifying agent. When the above clarifying agents are present alone or in combination, the upper limit of the content thereof is preferably 0.5%, more preferably 0.2%. In some embodiments, one or more of the above-described clarifying agents is present in an amount of about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%.
Other components not mentioned above, such as P, can be added in small amounts as required within the range that does not impair the glass properties of the present invention 2 O 5 、Bi 2 O 3 、Ta 2 O 5 、TeO 2 And Ga 2 O 3 The components are preferably contained in an amount of not more than 4% by weight, more preferably not more than 2% by weight, still more preferably not more than 1% by weight, and still more preferably not more than P alone or in combination 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or Ga 2 O 3 。
< component not to be contained >
In the glass of the present invention, V, cr, mn, fe, co, ni, cu, ag and oxides of transition metals such as Mo are colored even when they are contained in small amounts, either alone or in combination, and absorb at a specific wavelength in the visible light range, so that the property of the present invention of improving the visible light transmittance effect is impaired, and therefore, in particular, an optical glass having a wavelength transmittance in the visible light range is preferably practically not contained.
Th, cd, tl, os, be and Se oxides have a tendency to be used in a controlled manner as harmful chemical substances in recent years, and are required to provide environmental protection not only in the glass manufacturing process but also in the processing steps and disposal after production. Therefore, in the case where the influence on the environment is emphasized, it is preferable that they are not substantially contained except for unavoidable mixing. As a result, the optical glass becomes practically free from environmental pollutants. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures against the environment. Meanwhile, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
The term "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the optical glass of the present invention; however, it is also within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing optical glass that are not intentionally added, and that may be present in small or trace amounts in the final optical glass.
The properties of the optical glass of the present invention will be described below:
< refractive index and Abbe number >
Refractive index of optical glass (n) d ) With Abbe number (v) d ) Tested according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n d ) It is 1.88 or more, preferably 1.89 to 1.95, more preferably 1.90 to 1.94, and still more preferably 1.91 to 1.935.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) 30 or less, preferably 28 or less, more preferably 20 to 27, still more preferably 21 to 26, still more preferably 22 to 25.
< coloring degree >
The glass of the present invention has a coloring degree (lambda) for short-wave transmission spectrum characteristics 70 And lambda (lambda) 5 ) And (3) representing. Lambda (lambda) 70 Refers to the wavelength corresponding to when the glass transmittance reaches 70%. Lambda (lambda) 70 Is to measure spectral transmittance in a wavelength range from 280nm to 700nm and to exhibit a wavelength of 70% transmittance using glass having a thickness of 10.+ -. 0.1mm having two opposite planes which are parallel to each other and optically polished. The spectral transmittance or transmittance is the intensity I at right angles to the surface of the glass in Transmits through glass and emits intensity I from a plane out In the case of light passing through I out /I in The indicated amounts, and also the transmittance of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glass, λ 70 The small value of (2) means that the glass itself is extremely little colored and the light transmittance is high.
In some embodiments, λ of the optical glass of the present invention 70 Is 460nm or less, preferably lambda 70 Is 450nm or less, more preferably lambda 70 Is 440nm or less.
In some embodiments, λ of the optical glass of the present invention 5 Is 400nm or less, preferably lambda 5 Is 390nm or less, more preferably lambda 5 Is 380nm or less.
< stability against acid action >
Acid action resistance stability of optical glass (D A ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the acid action resistance stability (D A ) More than 2 kinds, preferably 1 kind.
< stability against Water action >
Stability against Water action of optical glass (D W ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the water resistance stability (D W ) More than 2 kinds, preferably 1 kind.
< crystallization upper limit temperature >
The crystallization performance of the glass is measured by adopting a gradient temperature furnace method, the glass is manufactured into a sample with the thickness of 180 multiplied by 10mm, the side surface is polished, the glass is put into a furnace with a temperature gradient (10 ℃/cm) and heated to 1300 ℃ (the temperature of the highest temperature zone) for 4 hours, then the glass is taken out and naturally cooled to the room temperature, the crystallization condition of the glass is observed under a microscope, and the highest temperature corresponding to the occurrence of the crystal of the glass is the crystallization upper limit temperature of the glass.
In some embodiments, the upper crystallization limit temperature of the optical glass of the present invention is 1180 ℃ or less, preferably 1160 ℃ or less, and more preferably 1140 ℃ or less.
< Young's modulus >
Young's modulus (E) of the glass is obtained by testing longitudinal wave speed and transverse wave speed by adopting ultrasonic waves and then calculating according to the following formula.
G＝V S 2 ρ
Wherein: e is Young's modulus, pa;
g is the shear modulus, pa;
V T is transverse wave speed, m/s;
V S is longitudinal wave speed, m/s;
ρ is the density of the glass, g/cm 3 。
In some embodiments, the Young's modulus (E) of the optical glass of the present invention is 9500×10 7 Preferably 10000X 10 or more per Pa 7 Preferably 10500×10 or more per Pa 7 and/Pa or more.
< coefficient of thermal expansion >
Coefficient of thermal expansion (. Alpha.) of optical glass 100～300℃ ) The data of 100-300 ℃ are tested according to the method specified in GB/T7962.16-2010.
The optical glass of the present invention has a coefficient of thermal expansion (. Alpha.) of 100～300℃ ) 110X 10 -7 Preferably 105X 10, K or less -7 Preferably less than or equal to K, more preferably 100X 10 -7 and/K or below.
< Density >
The density (ρ) of the optical glass was measured according to the method prescribed in GB/T7962.20-2010.
In some embodiments, the optical glass of the present invention has a density (ρ) of 4.30g/cm 3 Hereinafter, it is preferably 4.20g/cm 3 Hereinafter, it is more preferably 4.10g/cm 3 The following is given.
< abrasion degree >
Abrasion degree (F) of optical glass A ) The abrasion loss of the sample and the abrasion loss (volume) of the standard sample (H-K9 glass) are multiplied by 100 under the identical conditions, and the values are expressed as follows:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
wherein: v-the volume abrasion of the sample to be measured;
V 0 -standard sample volume attrition;
w is the mass abrasion quantity of the sample to be measured;
W 0 -standard sample mass abrasion;
ρ -the measured sample density;
ρ 0 standard sample density.
In some embodiments, the abrasiveness (F A ) It is 150 or more, preferably 180 or more, more preferably 200 to 300.
< relative partial Dispersion >
The relative partial dispersion for wavelengths x and y is represented by the following formula (1):
P x,y ＝(n x -n y )/(n F -n C ) (1)
according to Abbe's number formula, the following formula (2) is true for most of so-called "normal glasses" (hereinafter H-K6 and F4 are selected as "normal glasses")
P x,y ＝m x,y ·v d +b x,y (2)
The linear relationship is represented by P x,y Is in ordinate, v d Represented by the abscissa, where m x,y Is a slope, b x,y Is the intercept.
It is known that correction of the secondary spectrum, i.e. achromatizing to more than two wavelengths, requires at least one glass which does not correspond to formula (2) above (i.e. P x,y Empirical formula for the deviation of the value from the Abbe number) by ΔP x,y Representation, then each P x,y -v d The point is shifted by ΔP with respect to the "normal line" conforming to the above formula (2) x,y The amount of ΔP of each glass x,y The numerical value can be obtained by the following formula (3):
P x,y ＝m x,y ·v d +b x,y +ΔP x,y (3)
thus, the relative partial dispersion (P g,F ) The calculation formula of (2) is as follows:
P g,F ＝(n g -n F )/(n F -n C ) (4)
in some embodiments, the relative partial dispersion (P g,F ) From 0.6000 to 0.6400, preferably from 0.6100 to 0.6300, more preferably from 0.6150 to 0.6250.
< Secondary compression anti-crystallization Property >
The testing method of the secondary compression type crystallization resistance comprises the following steps: cutting sample glass into 20×20×10mm, and placing at temperature T g Preserving heat for 15-30 minutes in a muffle furnace with the temperature of between 200 and 250 ℃, taking out and cooling, and observing whether crystals exist on the surface and the inside of the glass or are opacified. If the glass sample is free of opacification and/or crystals, the secondary compression type crystallization resistance of the glass is excellent.
[ method of production ]
The manufacturing method of the optical glass comprises the following steps: the glass of the invention is produced by adopting conventional raw materials and processes, including but not limited to oxide, hydroxide, fluoride, various salts (carbonate, nitrate, sulfate, phosphate, metaphosphate) and the like as raw materials, after being proportioned according to a conventional method, the proportioned furnace charge is put into a smelting furnace (such as a platinum crucible) with the temperature of 1000-1400 ℃ for smelting, and after clarification and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mould and annealed. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and optical element ]
The optical glass thus produced may be used to produce a glass preform by direct drop molding, grinding, or compression molding such as hot press molding. That is, the glass preform may be produced by directly precision drop molding a molten optical glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from an optical glass, and then performing hot press molding and polishing on the preform. The means for producing the glass preform is not limited to the above-described means.
As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for performing hot press molding, precision press molding, and the like to produce optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by an optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms having high optical value.
Examples of the lens include 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, each of which has a spherical or aspherical lens surface.
[ optical instrument ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, image pickup equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of optical glass >
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 1 to 4 were obtained by using the above-described optical glass manufacturing method. The characteristics of each glass were measured by the test method of the present invention, and the measurement results are shown in tables 1 to 4. In the secondary press-molding crystallization resistance test of tables 1 to 4, according to the above test method, glass was marked as "a" without opalescence and without crystal particles on both the surface and inside, glass was marked as "B" without opalescence and without crystal particles on the inside but with crystal particles on the surface, glass was marked as "C" without opalescence and with 1 to 10 crystal particles inside, glass was marked as "D" without opalescence and with 10 to 20 crystal particles inside, and opalescence or dense crystal particles inside were marked as "x".
Table 1.
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Table 2.
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Table 3.
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Table 4.
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< example of glass preform >
The glasses obtained in examples 1 to 23 were subjected to polishing, hot press molding, and press molding such as precision press molding to prepare preforms of various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, prisms, and the like.
< example of optical element >
The glass preforms obtained in the above examples were annealed, and fine-tuning was performed while reducing deformation of the inside of the glass, so that optical characteristics such as refractive index reached a desired value.
Next, each preform was ground and polished to produce 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. The surface of the obtained optical element may be coated with an antireflection film.
< example of optical instrument >
The optical element manufactured by the above-described optical element embodiments can be used for, for example, imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for imaging devices and apparatuses in the vehicle field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims (14)

1. The optical glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 ：12～35％；
Nb 2 O 5 +TiO 2 +WO 3 ：25～55％；BaO+SrO+CaO+MgO：16～50％；ZnO：0～10％；Ln 2 O 3 ：0～10％；ZrO 2 :0 to 10 percent, wherein B 2 O 3 /SiO 2 Is 0.4 or less, (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is 0.5 to 2.2,
(ZnO+SrO+Ln 2 O 3 )/SiO 2 is 0.7 or less, ln is 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the above, the refractive index n of the optical glass d An Abbe number v of 1.88 or more d Is 30 or less.
2. The optical glass according to claim 1, further comprising, in weight percent: r is R 2 O: 0-10%; and/or Al 2 O 3 : 0-5%; and/or clarifying agent: 0 to 1 percent, wherein R is 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more of the following.
3. The optical glass according to claim 1 or 2, characterized in that its composition is expressed in weight percent, wherein: nb (Nb) 2 O 5 BaO is 0.2 to 1.2, preferably Nb 2 O 5 BaO is 0.2 to 1.0, more preferably Nb 2 O 5 BaO is 0.25 to 0.9, nb is more preferable 2 O 5 BaO is 0.3-0.8; and/or TiO 2 /(Nb 2 O 5 +ZrO 2 ) From 0.6 to 5.5, preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) From 0.7 to 4.0, more preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) From 0.8 to 3.0, tiO being further preferred 2 /(Nb 2 O 5 +ZrO 2 ) 1.0 to 2.5; and/or SiO 2 /(Nb 2 O 5 +TiO 2 ) From 0.3 to 1.3, preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) From 0.35 to 1.0, more preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.4 to 0.8.
4. The optical glass according to claim 1 or 2, characterized in that its composition is expressed in weight percent, wherein: b (B) 2 O 3 /SiO 2 From 0.01 to 0.3, preferably B 2 O 3 /SiO 2 0.03 to 0.2; and/or (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.6 or less, preferably (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.5 or less, more preferably (ZnO+SrO+Ln) 2 O 3 )/SiO 2 Is 0.3 or less; and/or (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.6 to 2.0, preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) of 0.8 to 1.8, more preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 +CaO+BaO) is 0.9 to 1.5.
5. The optical glass according to claim 1 or 2, characterized in that its composition is expressed in weight percent, wherein: siO (SiO) 2 +B 2 O 3 :15 to 30%, preferably SiO 2 +B 2 O 3 : 18-25%; and/or Nb 2 O 5 +TiO 2 +WO 3 :25 to 50%, preferably Nb 2 O 5 +TiO 2 +WO 3 : 30-45%; and/or bao+sro+cao+mgo:20 to 50%, preferably BaO+SrO+CaO+MgO: 25-40%; and/or ZnO:0 to 5%, preferably ZnO:0 to 2 percent; and/or Ln 2 O 3 :0 to 9%, preferably Ln 2 O 3 : 0-7%; and/or ZrO 2 :1 to 8%, preferably ZrO 2 : 2-7%; and/or R 2 O:0 to 6%, preferably R 2 O:0.5 to 5 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of R 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more of the following.
6. The optical glass according to claim 1 or 2, characterized in that its composition is expressed in weight percent, wherein: siO (SiO) 2 :12 to 30%, preferably SiO 2 :15 to 25%, more preferably SiO 2 : 16-23%; and/or Nb 2 O 5 :6 to 20%, preferably Nb 2 O 5 :7 to 18%, more preferably Nb 2 O 5 : 8-17%; and/or TiO 2 :15 to 35%, preferably TiO 2 :18 to 32%, more preferably TiO 2 : 20-30%; and/or BaO: 15-35%, preferably BaO:18 to 32%, more preferably BaO: 20-30%; and/or CaO:0 to 12%, preferably CaO:1 to 9%, more preferably CaO: 3-7%; and/or B 2 O 3 :0 to 6%, preferably B 2 O 3 :0.1 to 5%, more preferably B 2 O 3 :0.5 to 4 percent; and/or WO 3 ：0～10％Preferably WO 3 : from 0 to 5%, more preferably WO 3 :0 to 2 percent; and/or SrO: 0-8%, preferably SrO:0 to 4%, more preferably SrO:0 to 2 percent; and/or MgO:0 to 8%, preferably MgO:0 to 4%, more preferably MgO:0 to 2 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 2%, more preferably Li 2 O:0 to 1 percent; and/or Na 2 O:0 to 8%, preferably Na 2 O:0 to 6%, more preferably Na 2 O:0.5 to 5 percent; and/or K 2 O:0 to 5%, preferably K 2 O:0 to 3%, more preferably K 2 O：0～2％。
7. The optical glass according to claim 1 or 2, characterized in that its composition is expressed in weight percent, wherein: na (Na) 2 O/CaO is 5.0 or less, preferably Na 2 O/CaO is 0.01 to 3.0, more preferably Na 2 0.05 to 2.5 percent of O/CaO; and/or Li 2 O/B 2 O 3 Is 0.5 or less, preferably Li 2 O/B 2 O 3 Is 0.3 or less, more preferably Li 2 O/B 2 O 3 Is 0.1 or less, more preferably Li 2 O/B 2 O 3 Is 0.05 or less; and/or 10 xLi 2 O/Nb 2 O 5 Is 0.7 or less, preferably 10 xLi 2 O/Nb 2 O 5 Is 0.4 or less, more preferably 10×Li 2 O/Nb 2 O 5 Is 0.2 or less.
8. The optical glass according to claim 1 or 2, characterized in that it further comprises, in weight percent: not more than 4% of P 2 O 5 Preferably not more than 2% P 2 O 5 More preferably, not more than 1% P 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% Bi 2 O 3 Preferably not more than 2% Bi 2 O 3 More preferably not more than 1% Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% Ta 2 O 5 Preferably not more than 2% Ta 2 O 5 More preferably not more than 1% Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% TeO 2 Preferably not more than 2% TeO 2 More preferably not more than 1% TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or not more than 4% Ga 2 O 3 Preferably not more than 2% Ga 2 O 3 More preferably not more than 1% Ga 2 O 3 。
9. The optical glass according to claim 1 or 2, wherein the optical glass does not contain ZnO; and/or does not contain Li 2 O; and/or does not contain SrO; and/or does not contain MgO; and/or does not contain P 2 0 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Gd 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Y 2 O 3 。
10. The optical glass according to claim 1 or 2, wherein the refractive index n of the optical glass d 1.89 to 1.95, preferably 1.90 to 1.94, more preferably 1.91 to 1.935; abbe number v d 20 to 27, more preferably 21 to 26, and still more preferably 22 to 25.
11. The optical glass according to claim 1 or 2, wherein λ of the optical glass 70 Is 460nm or less, preferably lambda 70 Is 450nm or less, more preferably lambda 70 440nm or less; and/or lambda 5 Is 400nm or less, preferably lambda 5 Is 390nm or less, more preferably lambda 5 380nm or less; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or stability against water action D W More than 2 types, preferably 1 type; and/or the upper crystallization limit temperature is 1180 ℃ or lower, preferably 1160 ℃ or lower, more preferably 1140 ℃ or lower; and/or Young's modulus E of 9500×10 7 Preferably 10000X 10 or more per Pa 7 Preferably 10500×10 or more per Pa 7 The pressure of the mixture is higher than/Pa; and/or coefficient of thermal expansion alpha 100～300℃ 110X 10 -7 Preferably 105X 10, K or less -7 Preferably less than or equal to K, more preferably 100X 10 -7 and/K or below; density ρ of 4.30g/cm 3 Hereinafter, it is preferably 4.20g/cm 3 Hereinafter, it is more preferably 4.10g/cm 3 The following are set forth; and/or abrasion degree F A 150 or more, preferably 180 or more, more preferably 200 to 300; and/or relative partial dispersion P g,F From 0.6000 to 0.6400, preferably from 0.6100 to 0.6300, more preferably from 0.6150 to 0.6250.
12. A glass preform produced by using the optical glass according to any one of claims 1 to 11.
13. An optical element, characterized in that it is made of the optical glass according to any one of claims 1 to 11 or made of the glass preform according to claim 12.
14. An optical device comprising the optical glass according to any one of claims 1 to 11 or the optical element according to claim 13.
CN202311805778.5A 2021-09-07 2021-09-07 Optical glass and optical element Pending CN117756402A (en)

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