CN113582537B - High-refraction high-dispersion optical glass - Google Patents
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- CN113582537B CN113582537B CN202111046975.4A CN202111046975A CN113582537B CN 113582537 B CN113582537 B CN 113582537B CN 202111046975 A CN202111046975 A CN 202111046975A CN 113582537 B CN113582537 B CN 113582537B
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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
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
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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
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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Abstract
The invention provides high-refraction high-dispersion optical glass, which comprises the following components in percentage by weight: siO 2 2 ：11～30％；Nb 2 O 5 ：6～20％；TiO 2 ：15～35％；BaO：15～35％；CaO：1～12％；ZrO 2 :1 to 10% of Nb, wherein 2 O 5 The ratio of/BaO is 0.2-1.2. Through reasonable component design, the optical glass obtained by the invention has higher refractive index and dispersion, and simultaneously has lower thermal expansion coefficient, thereby meeting the application of high-performance photoelectric products.
Description
Technical Field
The invention relates to optical glass, in particular to high-refraction high-dispersion optical glass with a low thermal expansion coefficient.
Background
In recent years, with the development of fields such as photoelectric information and digital display, there has been a demand for downsizing, weight reduction, and high performance of optical elements used in optical systems. The high-refraction high-dispersion optical glass can be coupled with low-dispersion optical glass for use, so that chromatic aberration and secondary spectrum are effectively eliminated, the optical total length of a lens can be effectively shortened, and an imaging system is miniaturized, therefore, the glass has wide application prospect. The optical glass is easy to break in the processing process due to the larger thermal expansion coefficient, and the yield of the glass is reduced. On the other hand, an excessively large thermal expansion coefficient leads to deterioration in the thermal shock resistance of the glass, thereby limiting the application of the optical glass. Therefore, the development of high-refractive-index and high-dispersion optical glass with a low thermal expansion coefficient plays an important role in the development of high-performance photoelectric products.
Disclosure of Invention
The technical problem to be solved by the invention is to provide high-refraction high-dispersion optical glass with a lower thermal expansion coefficient.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) The high-refraction high-dispersion optical glass comprises the following components in percentage by weight: siO 2 2 ：11～30％；Nb 2 O 5 ：6～20％；TiO 2 ：15～35％；BaO：15～35％；CaO：1～12％；ZrO 2 :1 to 10% of Nb, wherein 2 O 5 The ratio of/BaO is 0.2-1.2.
(2) The high-refractive-index and high-dispersion optical glass according to (1), which comprises the following components in percentage by weight: b is 2 O 3 :0 to 6 percent; and/or WO 3 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or R 2 O:0 to 10 percent; and/or SrO:0 to 8 percent; and/or MgO:0 to 8 percent; and/or Ln 2 O 3 :0 to 10 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, wherein Ln is 2 O 3 Is 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 Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
(3) High refractive index high dispersive optical glass containing SiO 2 、Nb 2 O 5 、TiO 2 BaO as an essential component, the components of which are expressed in weight percent, wherein Nb 2 O 5 The ratio of BaO to n is 0.2-1.2, the refractive index n of the high-refraction high-dispersion optical glass d Is more than 1.90, and has Abbe number v d A coefficient of thermal expansion of 28 or less, alpha 100～300℃ Is 110 x 10 -7 The ratio of the sulfur to the sulfur is below K.
(4) The high-refractive-index and high-dispersion optical glass according to (3), which comprises the following components in percentage by weight: siO 2 2 :11 to 30 percent; and/or Nb 2 O 5 :6 to 20 percent; and/or TiO 2 :15 to 35 percent; and/or BaO:15 to 35 percent; and/or CaO:1 to 12 percent; and/or ZrO 2 :1 to 10 percent; and/or B 2 O 3 :0 to 6 percent; and/or WO 3 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or R 2 O:0 to 10 percent; and/or SrO:0 to 8 percent; and/or MgO:0 to 8 percent; and/or Ln 2 O 3 :0 to 10 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, wherein Ln is 2 O 3 Is 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 Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
(5) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which has a composition satisfying, in terms of weight percentage, one or more of the following 6 conditions:
1)Nb 2 O 5 a/BaO of 0.2 to 1.0, preferably Nb 2 O 5 A BaO of 0.25 to 0.9, more preferably Nb 2 O 5 The ratio of/BaO is 0.3-0.8;
2)TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.6 to 5.5, preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.7 to 4.0, more preferably TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.8 to 3.0, and TiO is more preferable 2 /(Nb 2 O 5 +ZrO 2 ) 1.0 to 2.5;
3)SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.3 to 1.3, preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.35 to 1.0, more preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.4 to 0.8;
4)B 2 O 3 /SiO 2 is 0.4 or less, preferably B 2 O 3 /SiO 2 Is 0.01 to 0.3, more preferably B 2 O 3 /SiO 2 0.03 to 0.2;
5)(ZnO+SrO+Ln 2 O 3 )/SiO 2 is 0.7 or less, preferably (ZnO + SrO + Ln) 2 O 3 )/SiO 2 Is 0.6 or less, more preferably (ZnO + SrO + Ln) 2 O 3 )/SiO 2 Is 0.5 or less, and (ZnO + SrO + Ln) is more preferable 2 O 3 )/SiO 2 Is 0.3 or less;
6)(SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.5 to 2.2, preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.6 to 2.0, more preferably (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.8 to 1.8, and (SiO) is more preferable 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.9 to 1.5.
(6) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: siO 2 2 :15 to 25%, preferably SiO 2 :16 to 23 percent; and/or Nb 2 O 5 :7 to 18%, preferably Nb 2 O 5 :8 to 17 percent; and/or TiO 2 :18 to 32%, preferably TiO 2 :20 to 30 percent; and/or BaO:18 to 32%, preferably BaO:20 to 30 percent; and/or ZrO 2 :2 to 8%, preferably ZrO 2 :2 to 7 percent; and/or B 2 O 3 :0.1 to 5%, preferably B 2 O 3 :0.5 to 4 percent; and/or WO 3 :0 to 2%, preferably WO 3 :0 to 1 percent; and/or ZnO:0 to 5%, preferably ZnO:0 to 2 percent; and/or SrO:0 to 4%, preferably SrO:0 to 2 percent; and/or CaO:2 to 9%, preferably CaO:3 to 7 percent; and/or MgO:0 to 4%, preferably MgO:0 to 2 percent; and/or Ln 2 O 3 :0 to 9%, preferably Ln 2 O 3 :0 to 7 percent; 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 a clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent of the total weight of the catalyst, wherein Ln is 2 O 3 Is 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 Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
(7) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which comprisesExpressed by weight percentage, wherein: 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％。
(8) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which 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, and Na is more preferable 2 O/CaO is 0.05 to 2.5; 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, and Li is more preferable 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 × Li 2 O/Nb 2 O 5 Is 0.4 or less, more preferably 10 XLi 2 O/Nb 2 O 5 Is 0.2 or less.
(9) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which comprises, in terms of weight percent, the following components: not more than 4% of P 2 O 5 Preferably not more than 2% of P 2 O 5 More preferably not more than 1% of P 2 O 5 (ii) a And/or not more than 4% of Bi 2 O 3 Preferably not more than 2% of Bi 2 O 3 More preferably not more than 1% of Bi 2 O 3 (ii) a And/or not more than 4% of Ta 2 O 5 Preferably not more than 2% Ta 2 O 5 More preferably not more than 1% of Ta 2 O 5 (ii) a And/or not more than 4% of TeO 2 Preferably not more than 2% of TeO 2 More preferably not more than 1% of TeO 2 (ii) a 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% of Ga 2 O 3 。
(10) According to (1)The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which does not contain ZnO; and/or do not contain Li 2 O; and/or does not contain P 2 0 5 (ii) a And/or does not contain Bi 2 O 3 (ii) a And/or does not contain Ta 2 O 5 (ii) a And/or does not contain TeO 2 (ii) a And/or does not contain WO 3 。
(11) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), wherein the refractive index n of the high-refractive-index, high-dispersion optical glass d 1.90 to 1.96, preferably 1.91 to 1.95, more preferably 1.915 to 1.93; abbe number v d 20 to 28, preferably 21 to 27, more preferably 22 to 26.
(12) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), wherein λ of the high-refractive-index, high-dispersion optical glass is 70 Is 450nm or less, preferably lambda 70 445nm or less, more preferably λ 70 Is 440nm or less; and/or lambda 5 Is 390nm or less, preferably lambda 5 Is 385nm or less, more preferably lambda 5 Is 380nm or less; and/or stability against acid action D A Is 2 or more, preferably 1; and/or stability against water action D W Is 2 or more, preferably 1; and/or the upper limit temperature of crystallization is 1180 ℃ or lower, preferably 1160 ℃ or lower, more preferably 1140 ℃ or lower; and/or a Young's modulus E of 9800X 10 7 A pressure of 10000X 10 or more, preferably 7 A value of 10500X 10 or more, more preferably,/Pa 7 More than Pa; and/or coefficient of thermal expansion alpha 100～300℃ Is 110X 10 -7 Preferably 105X 10 or less,/K -7 A value of not more than K, more preferably 100X 10 -7 below/K; the density rho is 4.30g/cm 3 Below, it is preferably 4.20g/cm 3 Hereinafter, more preferably 4.10g/cm 3 The following; and/or degree of wear F A 150 or more, preferably 180 or more, more preferably 200 to 300; and/or relative partial dispersion P g,F Is 0.6000 to 0.6400, preferably 0.6100 to 0.6300, more preferably 0.6150 to 0.6250.
(13) A glass preform made of the high-refractive-index, high-dispersion optical glass according to any one of (1) to (12).
(14) An optical element made of the high-refractive-index, high-dispersion optical glass according to any one of (1) to (12), or the glass preform according to (13).
(15) An optical device comprising the high-refractive-index, high-dispersion optical glass according to any one of (1) to (12), or comprising the optical element according to (14).
The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has higher refractive index and dispersion, and simultaneously has lower thermal expansion coefficient, thereby meeting the application of high-performance photoelectric products.
Detailed Description
The embodiments of the high-refractive-index, high-dispersion optical glass of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the present invention is not limited to this. In the following, the high-refractive high-dispersive optical glass of the present invention is sometimes referred to simply as optical glass or glass.
[ high refractive index and high dispersive optical glass ]
The ranges of the components of the high-refractive high-dispersive optical glass according to the invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the high-refractive-index, high-dispersion optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
SiO 2 The network forming body of the glass of the present invention has the effects of maintaining the chemical stability of the glass and the viscosity suitable for the molding of the molten glass, improving the devitrification resistance of the glass, and reducing the erosion of the molten glass to the refractory. If SiO 2 The content is less than 11%, and the above effects are hardly obtained, so that SiO 2 The lower limit of the content of (b) is 11%, preferably 15%, more preferably 16%. If SiO 2 When the content of (B) is more than 30%, the glass-melting property is lowered and the transition temperature is raised. Thus, siO 2 The upper limit of the content of (B) is 30%, preferably 25%, more preferably 23%.
B 2 O 3 Can improve the thermal stability of glass, improve the meltability of glass, inhibit the rapid escape of gas during the melting of raw materials so as to avoid 'blow out', and contain a proper amount of glass which can be easily obtained without residual molten raw materials of glass, but when B is 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 (b) is 6% or less, preferably 0.1 to 5%, more preferably 0.5 to 4%.
In some embodiments of the invention, B is 2 O 3 Content of (D) and SiO 2 Ratio B between contents of 2 O 3 /SiO 2 The content of the glass is controlled to be less than 0.4, which 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 0.01-0.3, the Young modulus and the abrasion degree of the glass are also favorable to be optimized. Therefore, B is more preferable 2 O 3 /SiO 2 Is 0.01 to 0.3, and B is more preferably 2 O 3 /SiO 2 0.03-0.2.
Nb 2 O 5 The high-refractive-index high-dispersion component can improve the refractive index and the devitrification resistance of the glass and reduce the thermal expansion coefficient of the glass, and the invention contains more than 6 percent of Nb 2 O 5 To obtain the above effects, nb is preferable 2 O 5 The content of (b) is 7% or more, more preferably 8% or more. If Nb 2 O 5 More than 20%, the thermal and chemical stability of the glass is lowered and the light transmittance is lowered, so that Nb in the present invention is 2 O 5 The upper limit of the content of (b) is 20%, preferably 18%, more preferably 17%.
TiO 2 Has the function of improving the refractive index and dispersion of the glass, can participate in the formation of a glass network, and can stabilize the glass and reduce the high-temperature viscosity of the glass by proper content. In the present invention, the content of TiO is 15% or more 2 To obtain the above effects, it is preferable to contain 18% or more of TiO 2 More preferably, it contains 20% or more of TiO 2 . If TiO 2 When the content exceeds 35%, the glass tends to be more devitrified, the transition temperature is increased, and the glass tends to be colored during press molding. Thus, tiO in the present invention 2 The content of (A) is 35% or less, preferably TiO 2 The content of (b) is 32% or less, more preferably 30% or less.
In some embodiments of the invention, the SiO is prepared by reacting SiO 2 Content of (b) and Nb 2 O 5 And TiO 2 2 Total content of (2) Nb 2 O 5 +TiO 2 Ratio of between SiO 2 /(Nb 2 O 5 +TiO 2 ) The control is in the range of 0.3-1.3, the thermal expansion coefficient and the density of the glass can be reduced, and simultaneously, the glass can obtain proper abrasion degree and relative partial dispersion. Therefore, siO is preferable 2 /(Nb 2 O 5 +TiO 2 ) 0.3 to 1.3, more preferably SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.35 to 1.0, and SiO is more preferable 2 /(Nb 2 O 5 +TiO 2 ) 0.4 to 0.8.
WO 3 Can improve the refractive index and dispersion of the glass, but the effect is not as good as that of Nb 2 O 5 And TiO 2 And does not have a cost advantage and also causes a reduction in the light transmittance of the glass. Thus, WO in the present invention 3 The content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably notContaining WO 3 。
ZnO can adjust the refractive index and dispersion of the glass, reduce the transition temperature of the glass, if the content of ZnO exceeds 8 percent, the devitrification resistance of the glass is reduced, meanwhile, the high-temperature viscosity is small, the forming is difficult, and the thermal expansion coefficient and the refractive index temperature coefficient of the glass are increased. Accordingly, in the present invention, the ZnO content is 0 to 8%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, it is further preferred that no ZnO is present.
R 2 O(R 2 O is Li 2 O、Na 2 O、K 2 One or more of O) may lower the transition temperature of the glass, and when the content thereof exceeds 10%, the chemical stability of the glass is lowered. Thus, R 2 The content of O is 0 to 10%, preferably 0 to 6%, more preferably 0.5 to 5%.
Li 2 O lowers the glass transition temperature and improves the glass meltability, but when it is contained in a high amount, it is unfavorable for the chemical stability, devitrification 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 not to contain Li 2 O。
In some embodiments of the invention, the lithium ion battery is prepared by reacting Li 2 Content of O and B 2 O 3 Ratio between contents of Li 2 O/B 2 O 3 Below 0.5, the chemical stability and the secondary compression surface crystallization resistance of the glass can be improved, and the abrasion degree of the glass is optimized. Therefore, li is preferable 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, and Li is more preferable 2 O/B 2 O 3 Is 0.1 or less, and Li is more preferable 2 O/B 2 O 3 Is 0.05 or less.
In some embodiments of the invention, the composition is prepared by subjecting 10 × Li 2 O/Nb 2 O 5 Below 0.7, it is favorable to raise the chemical stability and secondary compression crystallization resistance of glass and raise the Young's modulus of glass. Therefore, 10 × Li is preferable 2 O/Nb 2 O 5 Is 0.7 or less, more preferably 10 XLi 2 O/Nb 2 O 5 Is 0.4 or less, and more preferably 10 × Li 2 O/Nb 2 O 5 Is 0.2 or less.
Na 2 O has an effect of improving the meltability of glass, can improve the glass melting effect, and can lower the glass transition temperature. If Na 2 The O content exceeds 8%, the chemical stability and weather resistance of the glass are lowered, and therefore Na 2 The content of O is 0 to 8%, preferably Na 2 The content of O is 0 to 6%, more preferably Na 2 The content of O is 0.5-5%.
K 2 O has an effect of improving the thermal stability and melting property of the glass, but the content thereof exceeds 5%, and the resistance to devitrification and chemical stability of the glass are deteriorated, so that K in the present invention 2 The content of O is 5% or less, preferably K 2 The content of O is 3% or less, more preferably 2% or less.
MgO can reduce the refractive index and melting temperature of the glass, but the refractive index of the glass cannot meet the design requirement when the content of MgO is excessive, the devitrification resistance and stability of the glass are reduced, and the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%.
CaO is helpful for adjusting the optical constants of the glass, improving the processability of the glass and reducing the density of the glass, but when the content of CaO is too large, the optical constants of the glass cannot meet the requirements and the devitrification resistance is deteriorated. Therefore, the CaO content is limited to 1 to 12%, preferably 2 to 9%, and more preferably 3 to 7%.
In some embodiments of the invention, na is controlled by 2 The ratio Na between the content of O and the content of CaO 2 The O/CaO is less than 5.0, and the anti-crystallization performance of the glass can be improved. Therefore, na is preferred 2 The O/CaO ratio is below 5.0. Further, by controlling Na 2 The O/CaO is in the range of 0.01-3.0, 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, and Na is more preferable 2 O/CaO of 0.05 to 2.5。
While SrO can adjust the refractive index and Abbe number of the glass, if the content is too large, the chemical stability of the glass is lowered and the cost of the glass is rapidly increased. Therefore, the SrO content is limited to 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%.
BaO is an essential component for adjusting the refractive index of the glass, improving the transmittance and strength of the glass in the present invention, and the above effect is not significant when the content thereof is less than 15%, and the lower limit of the content of BaO is preferably 18%, and the lower limit of the content of BaO is more preferably 20%. On the other hand, if the content of BaO exceeds 35%, the devitrification resistance and chemical stability of the glass deteriorate, and the density increases significantly. Therefore, the upper limit of the BaO content is 35%, preferably 32%, more preferably 30%.
In some embodiments of the invention, nb is controlled 2 O 5 And a ratio Nb between the contents of BaO 2 O 5 The content of/BaO is in the range of 0.2-1.2, so that the glass has excellent chemical stability and the thermal expansion coefficient of the glass is reduced. Therefore, nb is preferable 2 O 5 A BaO of 0.2 to 1.2, more preferably Nb 2 O 5 The ratio of/BaO is 0.2-1.0. Further, by controlling Nb 2 O 5 The content of/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 A BaO of 0.25 to 0.9, and Nb is more preferable 2 O 5 The ratio of/BaO is 0.3-0.8.
ZrO 2 Can improve the refractive index of the glass, adjust the dispersion and improve the devitrification resistance and the strength of the glass, and the invention contains more than 1 percent of ZrO 2 To obtain the above effects, zrO is preferable 2 The content of (A) is more than 2%. 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 in the glass are generated and the transmittance is reduced. Thus, zrO 2 The content is 10% or less, preferably 8% or less, and more preferably 7% or less.
In some embodiments of the invention, the TiO is controlled 2 Content of (2) and Nb 2 O 5 And ZrO 2 Total content of (B) Nb 2 O 5 +ZrO 2 TiO in the ratio of 2 /(Nb 2 O 5 +ZrO 2 ) In the range of 0.6-5.5, the crystallization resistance and the light transmittance of the glass are improved. Therefore, tiO is preferred 2 /(Nb 2 O 5 +ZrO 2 ) 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, the glass can also obtain proper abrasion degree and relative partial dispersion. Therefore, tiO is more preferable 2 /(Nb 2 O 5 +ZrO 2 ) 0.8 to 3.0, and TiO is more preferable 2 /(Nb 2 O 5 +ZrO 2 ) Is 1.0 to 2.5.
In some embodiments of the invention, the SiO is prepared by reacting SiO 2 And TiO 2 SiO in total content 2 +TiO 2 And Nb 2 O 5 、ZrO 2 Total content Nb of CaO and BaO 2 O 5 +ZrO 2 The ratio between + CaO + BaO (SiO) 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 And + CaO + BaO) is controlled within the range of 0.5-2.2, so that the glass forming stability and chemical stability of the glass can be improved, and the density of the glass can be reduced. Therefore, (SiO) is preferable 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 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 And + CaO + BaO) is in the range of 0.8-1.8, so that the secondary compression devitrification resistance and the Young modulus of the glass can be further improved. Therefore, (SiO) is more preferable 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.
Ln 2 O 3 (Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more) is a component for improving the refractive index and chemical stability of the glass by adding Ln 2 O 3 The content of (2) is controlled to 10% or less, and a decrease in devitrification resistance of the glass can be prevented, preferably Ln 2 O 3 The upper limit of the content range is 9%, and the more preferable upper limit is 7%. In some embodiments, ln is preferred 2 O 3 Is La 2 O 3 。
In some embodiments of the invention, the ZnO, srO and Ln are mixed 2 O 3 ZnO + SrO + Ln in total 2 O 3 With SiO 2 Ratio between contents of (ZnO + SrO + Ln) 2 O 3 )/SiO 2 And the control below 0.7 is favorable for 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 When the amount is 0.5 or less, the thermal expansion coefficient of the glass can be reduced. 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.
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 melting resistance of the glass are lowered, so that the content is 5% or less, preferably 3% or less, more preferably 2% or less.
In some embodiments, the glasses of the present invention may also contain 0-1% fining agents to improve the bubble removal capability of the glass. Such fining agents include, but are not limited to, sb 2 O 3 、SnO 2 SnO and CeO 2 Preferably Sb 2 O 3 As a clarifying agent. The upper limit of the content of the above-mentioned clarifying agent is preferably 0.5%, more preferably 0.2%, when it is present alone or in combination.
Without damaging the glass of the inventionWithin the range of the properties, other components not mentioned above, such as P, can be added in small amounts as required 2 O 5 、Bi 2 O 3 、Ta 2 O 5 、TeO 2 And Ga 2 O 3 The content of the components, either individually or in total, is preferably not more than 4%, more preferably not more than 2%, still more preferably not more than 1%, and still more preferably not containing P 2 O 5 (ii) a And/or Bi 2 O 3 (ii) a And/or Ta 2 O 5 (ii) a And/or TeO 2 (ii) a And/or Ga 2 O 3 。
< Components not to be contained >
In the glass of the present invention, even when the glass contains a small amount of oxides of transition metals such as V, cr, mn, fe, co, ni, cu, ag, and Mo singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the effect of the present invention to improve the visible light transmittance.
In recent years, oxides of Th, cd, tl, os, be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures. Meanwhile, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.
The properties of the optical glass of the present invention will be described below:
< refractive index and Abbe number >
Refractive index (n) of optical glass d ) And Abbe number (. Nu.) d ) The test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n) of the optical glass of the present invention d ) The upper limit of (a) is 1.96, the preferable upper limit is 1.95, and the more preferable upper limit is 1.93.
In some embodiments, the refractive index (n) of the optical glass of the present invention d ) The lower limit of (b) is 1.90, preferably 1.91, more preferably 1.915.
In some embodiments, the Abbe number (v) of the optical glass of the present invention d ) The upper limit of (2) is 28, preferably 27, more preferably 26, and still more preferably 25.
In some embodiments, the Abbe number (v) of the optical glass of the present invention d ) The lower limit of (2) is 20, preferably 21, more preferably 22.
< degree of coloration >
Coloring degree (. Lamda.) for short-wave transmission spectral characteristics of the glass of the present invention 70 And λ 5 ) And (4) showing. Lambda [ alpha ] 70 Refers to the wavelength corresponding to the glass transmittance of 70%. Lambda [ alpha ] 70 Is measured by measuring the spectral transmittance in a wavelength region from 280nm to 700nm using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished and exhibiting a wavelength of 70% transmittance. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glass in Light transmitted through the glass and having an intensity I emitted from a plane out Under the condition of light of (1) through out /I in The quantities expressed and also the transmission 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 glasses, λ 70 A small value of (a) means that the glass itself is colored very little,the light transmittance is high.
In some embodiments, the λ of the optical glass of the present invention 70 Is 450nm or less, preferably lambda 70 445nm or less, more preferably λ 70 Is 440nm or less.
In some embodiments, the λ of the optical glass of the present invention 5 Is 390nm or less, preferably lambda 5 Is 385nm or less, more preferably lambda 5 Is 380nm or less.
< stability against acid Effect >
Stability of acid resistance of optical glass (D) A ) (powder method) the test was carried out according to the method described in GB/T17129.
In some embodiments, the stability to acid action of the optical glasses of the invention (D) A ) Is 2 or more, preferably 1.
< stability against Water action >
Stability to Water of optical glass (D) W ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the optical glass of the present invention has stability to water effects (D) W ) Is 2 or more, preferably 1.
< upper limit temperature of crystallization >
The crystallization performance of the glass is measured by adopting a gradient temperature furnace method, the glass is made into a sample of 180 multiplied by 10mm, the side surface is polished, the sample is put into a furnace with a temperature gradient (10 ℃/cm) and heated to 1300 ℃ (the temperature of the highest temperature zone) for heat preservation for 4 hours, then the sample 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 crystals of the glass is the crystallization upper limit temperature of the glass.
In some embodiments, the optical glass of the present invention has an upper crystallization limit temperature of 1180 ℃ or lower, preferably 1160 ℃ or lower, and more preferably 1140 ℃ or lower.
< Young's modulus >
The Young's modulus (E) of the glass is obtained by measuring the longitudinal wave velocity and the transverse wave velocity of the glass by ultrasonic waves and calculating according to the following formula.
G＝V S 2 ρ
In the formula: e is Young's modulus, pa;
g is shear modulus, pa;
V T is the transverse wave velocity, m/s;
V S is the longitudinal wave velocity, m/s;
rho is the density of the glass, g/cm 3 。
In some embodiments, the optical glass of the present invention has a Young's modulus (E) of 9800X 10 7 A pressure of 10000X 10 or more, preferably 7 A value of 10500X 10 or more, more preferably,/Pa 7 More than Pa.
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of optical glass 100～300℃ ) The data at 100-300 ℃ were measured according to the method specified in GB/T7962.16-2010.
The coefficient of thermal expansion (. Alpha.) of the optical glass of the present invention 100～300℃ ) Is 110 x 10 -7 Preferably 105X 10 or less,/K -7 A value of not more than K, more preferably 100X 10 -7 The ratio of the sulfur to the sulfur is below K.
< Density >
The density (. Rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
In some embodiments, the optical glass of the present invention has a density (. Rho.) of 4.30g/cm 3 Hereinafter, it is preferably 4.20g/cm 3 Hereinafter, more preferably 4.10g/cm 3 The following.
< degree of abrasion >
Degree of abrasion (F) of optical glass A ) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the value is expressed by the following formula:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
in the formula: v, the volume abrasion loss of the measured sample;
V 0 -the abrasion loss by volume of the standard sample;
w is the abrasion loss of the quality of the sample to be measured;
W 0 -abrasion loss of standard sample mass;
rho is the density of the sample to be measured;
ρ 0 -standard sample density.
In some embodiments, the optical glass of the present invention has an abrasion degree (F) A ) Is 150 or more, preferably 180 or more, and 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)
the following formula (2) holds for most of the so-called "normal glasses" according to the Abbe number formula (hereinafter, H-K6 and F4 are used as "normal glasses")
P x,y ＝m x,y ·v d +b x,y (2)
This linear relationship is P x,y Is ordinate, v d Expressed on the abscissa, where m x,y Is a slope, b x,y Is the intercept.
It is known that the correction of the secondary spectrum, i.e. the achromatization of more than two wavelengths, requires at least one glass which does not conform to the above formula (2) (i.e. its P) x,y Value deviation from an empirical formula for abbe number) by Δ P x,y Indicates that each P is x,y -v d The point being shifted by Δ P with respect to a "normal line" corresponding to the above formula (2) x,y Amount of such a.DELTA.P of each glass x,y The numerical value can be obtained by the following equation (3):
P x,y ＝m x,y ·v d +b x,y +ΔP x,y (3)
therefore, from the above, relative partial dispersion (P) can be obtained g,F ) Is the following formula (4):
P g,F ＝(n g -n F )/(n F -n C ) (4)
in some embodiments, the relative partial dispersion (P) of the optical glasses of the present invention g,F ) Is 0.6000 to 0.6400, preferably 0.6100 to 0.6300, more preferably 0.6150 to 0.6250.
< Secondary compression type devitrification resistance >
The test method of the secondary compression type anti-crystallization performance comprises the following steps: the sample glass was cut into a size of 20X 10mm and put at a temperature T g And (4) preserving the heat in a muffle furnace at 200-250 ℃ for 15-30 minutes, taking out and cooling, and observing whether crystals exist on the surface and the inside of the glass or opacification occurs. If the glass sample has no opacities and/or crystals, the secondary compression crystallization resistance of the glass is excellent.
[ production method ]
The manufacturing method of the high-refraction high-dispersion 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 oxides, hydroxides, fluorides, various salts (carbonates, nitrates, sulfates, phosphates, metaphosphates) and the like as raw materials, the prepared furnace charge is put into a smelting furnace (such as a platinum crucible) with the temperature of 1000-1400 ℃ for smelting after being mixed according to a conventional method, and homogeneous molten glass without bubbles and undissolved substances is obtained after clarification and homogenization, and the molten glass is cast in a mould and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Glass preform and optical element
The glass preform can be made from the high-refractive high-dispersive optical glass produced by direct gob-casting, grinding, or press molding such as hot press molding. That is, the glass preform can be produced by directly precision-dropping a molten high-refractive high-dispersive optical glass to form a glass precision preform, or by producing a glass preform by mechanical processing such as grinding and polishing, or by producing a preform for press molding from a high-refractive high-dispersive optical glass, and then performing a reheat press molding on the preform and then performing a polishing process. Note that the means for producing the glass preform is not limited to the above means.
As described above, the high-refractive-index, high-dispersion 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 high-refractive-index, high-dispersion optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform and the optical element of the present invention are each formed of the above-described high-refractive high-dispersive optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by high-refractive-index, high-dispersion optical glass; the optical element of the present invention has excellent properties of high-refractive and high-dispersive optical glass, and can provide optical elements such as various lenses and prisms having high optical values.
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.
[ optical instruments ]
The optical element formed by the high-refraction high-dispersion optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< high refractive index high dispersive optical glass example >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, high-refractive high-dispersion optical glasses having compositions shown in tables 1 to 3 were obtained by the above-described method for producing high-refractive high-dispersion optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 3. In the secondary press type devitrification resistance tests in tables 1 to 3, according to the above-mentioned test methods, the glass is not opacified and has no crystal particles on the surface and inside and is denoted by "a", the glass is not opacified and has no crystal particles inside and has crystal particles on the surface and is denoted by "B" (the glass composition having crystal particles on the surface can be removed by grinding at the time of secondary press type of glass, but does not increase the grinding cost, and therefore, it is more preferable that there is no crystal particles inside and outside the glass), the glass is not opacified and has 1 to 10 crystal particles inside and is denoted by "C", the glass is not opacified and has 10 to 20 crystal particles inside and is denoted by "D", and the glass is denoted by "x" which opacified or densely crystallized particles inside are generated.
Table 1.
Table 2.
Table 3.
< glass preform example >
Various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses and plano-concave lenses, and preforms such as prisms were produced by press molding the glasses obtained in examples 1 to 18 of the high-refractive high-dispersive optical glass by means of, for example, grinding or hot press molding or precision press molding.
< optical element example >
The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to 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 a prism. The surface of the resulting optical element may be further coated with an antireflection film.
< optical Instrument embodiment >
The optical element obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.
Claims (30)
1. High-refractive-index and high-dispersive optical glass, characterized in that the glass comprises the following components in percentage by weight: siO 2 2 ：11～30％；Nb 2 O 5 ：6～20％；TiO 2 ：15～35％；BaO：15～35％；CaO：1～12％；ZrO 2 ：1～10％；ZnO：0～8％；SrO：0～8％；Ln 2 O 3 :0 to 10% of Nb 2 O 5 BaO is 0.2-1.2, (ZnO + SrO + Ln) 2 O 3 )/SiO 2 0.097 to 0.537, the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of (a).
2. A high-refractive-index, high-dispersive optical glass according to claim 1, characterized in that it further comprises, expressed in weight percent: b is 2 O 3 :0 to 6 percent; and/or WO 3 :0 to 5 percent; and/or R 2 O:0 to 10 percent; and/or MgO:0 to 8 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1%, wherein R is 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
3. High-refractive-index high-dispersion optical glass characterized by containing SiO 2 、Nb 2 O 5 、TiO 2 BaO as an essential component, the components of which are expressed in weight percent, wherein Nb 2 O 5 The ratio of/BaO is 0.2-1.2,
(ZnO+SrO+Ln 2 O 3 )/SiO 2 0.097 to 0.537, the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 Of high refractive index, high dispersion optical glass having a refractive index n d Is more than 1.90, and has Abbe number v d A coefficient of thermal expansion of 28 or less 100～300℃ Is 110 x 10 -7 and/K is less than or equal to.
4. A high-refractive-index, high-dispersive optical glass according to claim 3, characterized in that its composition, expressed in weight percentages, comprises: siO 2 2 :11 to 30 percent; and/or Nb 2 O 5 :6 to 20 percent; and/or TiO 2 :15 to 35 percent; and/or BaO:15 to 35 percent; and/or CaO:1 to 12 percent; and/or ZrO 2 :1 to 10 percent; and/or B 2 O 3 :0 to 6 percent; and/or WO 3 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or R 2 O:0 to 10 percent; and/or SrO:0 to 8 percent;and/or MgO:0 to 8 percent; and/or Ln 2 O 3 :0 to 10 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, wherein Ln is 2 O 3 Is 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 Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
5. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 6 conditions:
1)Nb 2 O 5 the ratio of/BaO is 0.2-1.0;
2)TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.6 to 5.5;
3)SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.3 to 1.3;
4)B 2 O 3 /SiO 2 is less than 0.4;
5)(ZnO+SrO+Ln 2 O 3 )/SiO 2 0.097 to 0.5;
6)(SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.5 to 2.2.
6. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 6 conditions:
1)Nb 2 O 5 the ratio of/BaO is 0.25-0.9;
2)TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.7 to 4.0;
3)SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.35 to 1.0;
4)B 2 O 3 /SiO 2 0.01 to 0.3;
5)(ZnO+SrO+Ln 2 O 3 )/SiO 2 0.097 to 0.3;
6)(SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.6 to 2.0.
7. A high-refractive-index, high-dispersive optical glass according to any of claims 1 to 4, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 5 conditions:
1)Nb 2 O 5 the ratio of/BaO is 0.3-0.8;
2)TiO 2 /(Nb 2 O 5 +ZrO 2 ) 0.8 to 3.0;
3)SiO 2 /(Nb 2 O 5 +TiO 2 ) 0.4 to 0.8;
4)B 2 O 3 /SiO 2 0.03 to 0.2;
5)(SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.8 to 1.8.
8. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 2 conditions:
1)TiO 2 /(Nb 2 O 5 +ZrO 2 ) 1.0 to 2.5;
2)(SiO 2 +TiO 2 )/(Nb 2 O 5 +ZrO 2 + CaO + BaO) is 0.9 to 1.5.
9. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it comprises, expressed in weight percent: siO 2 2 :15 to 25 percent; and/or Nb 2 O 5 :7 to 18 percent; and/or TiO 2 :18 to 32 percent; and/or BaO:18 to 32 percent; and/or ZrO 2 :2 to 8 percent; and/or B 2 O 3 :0.1 to 5 percent; and/or WO 3 :0 to 2 percent; and/or ZnO:0 to 5 percent; and/or SrO:0 to 4 percent; and/or CaO:2 to 9 percent; and/or MgO:0 to 4 percent; and/or Ln 2 O 3 :0 to 9 percent; and/or R 2 O:0 to 6 percent; and/or Al 2 O 3 :0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent, wherein Ln is 2 O 3 Is 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 Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
10. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it comprises, expressed in weight percent: siO 2 2 :16 to 23 percent; and/or Nb 2 O 5 :8 to 17 percent; and/or TiO 2 :20 to 30 percent; and/or BaO:20 to 30 percent; and/or ZrO 2 :2 to 7 percent; and/or B 2 O 3 :0.5 to 4 percent; and/or WO 3 :0 to 1 percent; and/or ZnO:0 to 2 percent; and/or SrO:0 to 2 percent; and/or CaO:3 to 7 percent; and/or MgO:0 to 2 percent; and/or Ln 2 O 3 :0 to 7 percent; and/or R 2 O:0.5 to 5 percent; and/or Al 2 O 3 :0 to 2 percent; and/or a clarifying agent: 0 to 0.2 percent, wherein Ln 2 O 3 Is 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 Sb as clarifier 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a).
11. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, having the composition, expressed in weight percentages, wherein: li 2 O:0 to 3 percent; and/or Na 2 O:0 to 8 percent; and/or K 2 O：0～5％。
12. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it has the composition, expressed in weight percentages, in which: li 2 O:0 to 2 percent; and/or Na 2 O:0 to 6 percent; and/or K 2 O：0～3％。
13. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it has the composition, expressed in weight percentages, in which: li 2 O:0 to 1 percent; and/or Na 2 O:0.5 to 5 percent; and/or K 2 O：0～2％。
14. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it has the composition, expressed in weight percentages, in which: na (Na) 2 O/CaO is 5.0 or less; and/or Li 2 O/B 2 O 3 Is less than 0.5; and/or 10 × Li 2 O/Nb 2 O 5 Is 0.7 or less.
15. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, having the composition, expressed in weight percentages, wherein: na (Na) 2 O/CaO is 0.01-3.0; and/or Li 2 O/B 2 O 3 Is 0.3 or less; and/or 10 xli 2 O/Nb 2 O 5 Is 0.4 or less.
16. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, having the composition, expressed in weight percentages, wherein: na (Na) 2 O/CaO is 0.05 to 2.5; and/or Li 2 O/B 2 O 3 Is 0.1 or less; and/or 10 × Li 2 O/Nb 2 O 5 Is 0.2 or less.
17. The high-refractive high-dispersive optical glass according to any of claims 1-4,the composite material is characterized by comprising the following components in percentage by weight: li 2 O/B 2 O 3 Is 0.05 or less.
18. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, further comprising, in terms of weight percent: not more than 4% of P 2 O 5 (ii) a And/or not more than 4% of Bi 2 O 3 (ii) a And/or not more than 4% Ta 2 O 5 (ii) a And/or not more than 4% of TeO 2 (ii) a And/or not more than 4% Ga 2 O 3 。
19. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, further comprising, in terms of weight percent: not more than 2% of P 2 O 5 (ii) a And/or not more than 2% of Bi 2 O 3 (ii) a And/or not more than 2% of Ta 2 O 5 (ii) a And/or not more than 2% of TeO 2 (ii) a And/or not more than 2% Ga 2 O 3 。
20. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it further comprises, in percentages by weight: not more than 1% of P 2 O 5 (ii) a And/or not more than 1% of Bi 2 O 3 (ii) a And/or not more than 1% Ta 2 O 5 (ii) a And/or not more than 1% of TeO 2 (ii) a And/or not more than 1% Ga 2 O 3 。
21. The high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refractive-index, high-dispersion optical glass contains no ZnO; and/or do not contain Li 2 O; and/or does not contain P 2 0 5 (ii) a And/or does not contain Bi 2 O 3 (ii) a And/or does not contain Ta 2 O 5 (ii) a And/or does not contain TeO 2 (ii) a And/or does not contain WO 3 。
22. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refractive-index, high-dispersion optical glass has a refractive index n d 1.90 to 1.96; abbe number v d Is 20 to 28.
23. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refractive-index, high-dispersion optical glass has a refractive index n d 1.91 to 1.95; abbe number v d Is 21 to 27.
24. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refractive-index, high-dispersion optical glass has a refractive index n d 1.915-1.93; abbe number v d Is 22 to 26.
25. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein λ of the high-refractive-index, high-dispersion optical glass is 70 Is 450nm or less; and/or lambda 5 Is 390nm or less; and/or stability against acid action D A Is more than 2 types; and/or stability against water action D W Is more than 2 types; and/or the upper limit temperature of crystallization is 1180 ℃ or lower; and/or a Young's modulus E of 9800X 10 7 More than Pa; and/or coefficient of thermal expansion alpha 100～300℃ Is 110X 10 -7 below/K; and/or a density rho of 4.30g/cm 3 The following; and/or degree of wear F A Is more than 150; and/or relative partial dispersion P g,F Is 0.6000 to 0.6400.
26. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein λ of the high-refractive-index, high-dispersion optical glass is 70 445nm or less; and/or lambda 5 Is 385nm or less; and/or stability against acid action D A Is in class 1; and/or stability against water action D W Is in class 1; and/or the upper limit temperature of crystallization is 1160 ℃ or lower; and/or a Young's modulus E of 10000X 10 7 Over Pa(ii) a And/or coefficient of thermal expansion alpha 100～300℃ Is 105 x 10 -7 below/K; and/or a density rho of 4.20g/cm 3 The following; and/or degree of wear F A Is more than 180; and/or relative partial dispersion P g,F Is 0.6100 to 0.6300.
27. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein λ of the high-refractive-index, high-dispersion optical glass is 70 Is 440nm or less; and/or lambda 5 Is 380nm or less; and/or the upper limit temperature of crystallization is 1140 ℃ or lower; and/or a Young's modulus E of 10500X 10 7 More than Pa; and/or coefficient of thermal expansion alpha 100～300℃ Is 100 x 10 -7 below/K; and/or a density rho of 4.10g/cm 3 The following; and/or degree of wear F A Is 200 to 300; and/or relative partial dispersion P g,F 0.6150-0.6250.
28. A glass preform made of the high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 27.
29. An optical element, characterized by being made of the high-refractive-index, high-dispersion optical glass of any one of claims 1 to 27, or the glass preform of claim 28.
30. An optical device comprising the high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 27 or comprising the optical element according to claim 29.
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| CN115010363A (en) * | 2022-06-01 | 2022-09-06 | 河北光兴半导体技术有限公司 | High-refractive-index glass composition, high-refractive-index glass, and preparation method and application thereof |
| CN115028353B (en) * | 2022-06-22 | 2023-08-08 | 成都光明光电有限责任公司 | Optical glass with negative anomalous dispersion |
| CN115286236A (en) * | 2022-07-25 | 2022-11-04 | 河北光兴半导体技术有限公司 | Glass composition, optical glass, and preparation method and application thereof |
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