CN114853334A - Optical glass, optical preform, optical element and optical instrument - Google Patents
Optical glass, optical preform, optical element and optical instrument Download PDFInfo
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- 239000005304 optical glass Substances 0.000 title claims abstract description 163
- 230000003287 optical effect Effects 0.000 title claims abstract description 55
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 48
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000008395 clarifying agent Substances 0.000 claims description 8
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 7
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 27
- 239000006185 dispersion Substances 0.000 abstract description 16
- 239000011521 glass Substances 0.000 description 74
- 238000004031 devitrification Methods 0.000 description 15
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 230000005499 meniscus Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- -1 platinum ions Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Abstract
The invention discloses optical glass, wherein the optical glass comprises 15-35 wt% of P 2 O 5 1 to 18% of Na 2 O+K 2 O, 10-25% of TiO 2 And 38-52% of Nb 2 O 5 And wherein Nb 2 O 5 /(K 2 O+Na 2 O) is in the range of 2.87 to 10.0. The invention also discloses an optical prefabricated member made of the optical glass, an optical element made of the optical glass or the optical prefabricated member, and an optical instrument comprising the optical glass or the optical element. The optical glass has high refractive index and high dispersion, and also has excellent chemical stability and bubble degree.
Description
The present application is a divisional application of the invention patent application entitled "optical glass, optical preform, optical element and optical instrument" with application number 201811472314.6, application date 2018, 12 and 03.
Technical Field
The present invention relates to glass, and more particularly, to optical glass, and an optical preform, an optical element, and an optical instrument made of the optical glass.
Background
With the continuous fusion of optics and electronic information science and new material science, the application of optical glass as a photoelectron base material in the technical fields of light transmission, light storage, photoelectric display and the like is rapidly advanced. In recent years, optical elements and optical instruments have been rapidly developed in terms of digitization, integration, and high definition, and higher demands have been made on the performance of optical glasses used for optical elements of optical instruments and devices.
The optical glass is likely to be corroded by the environment and various chemical reagents and liquid medicines during the use process, so the resistance of the optical glass to the corrosion, namely the chemical stability of the optical glass is very important for the use precision and the service life of the instrument. Furthermore, the presence of defects such as residual bubbles and foreign matter in the optical glass also significantly affects the use of the optical glass in optical glass, particularly in optoelectronic systems.
It is necessary to suppress the generation of defects such as bubbles and to improve the chemical stability of the optical glass while satisfying the refractive index and abbe number optical properties of the optical glass.
The optical glass has optical constants such as refractive index and Abbe number, can be processed and molded at lower temperature, and the finished optical glass has the characteristics of better chemical stability, low expansion rate and the like so as to meet the application of the optical glass in the field of photoelectrons. There is still a need for optical glasses having improved above-mentioned properties.
Disclosure of Invention
In view of the problems in the related art, the present invention provides an optical glass having good chemical stability and bubble degree while having optical constants such as high refractive index and high dispersion. The inventors of the present invention have found that the above-mentioned technical problems can be solved and the object of improving the chemical stability and the degree of blistering of an optical glass can be achieved by adjusting the weight percentages of the components constituting the optical glass and adjusting the ratios between the components.
In one aspect of the present invention, an optical glass is provided. The content of each component in the optical glass is calculated by weight percent based on the total weight of each component in the optical glassContains 15 to 35 percent of P in percentage by weight 2 O 5 1 to 18% of Na 2 O+K 2 O, 10-25% of TiO 2 And 38-52% of Nb 2 O 5 And Nb 2 O 5 /(K 2 O+Na 2 O) is in the range of 2.0 to 10.0.
In one embodiment, the optical glass of the present invention further comprises 0 to 5% of SiO based on the total weight of the components in the optical glass 2 And/or 0 to 5% of ZrO 2 And/or 0-8% of ZnO and/or 0-5% of B 2 O 3 And/or 0 to 6% of Al 2 O 3 And/or 0 to 8% of WO 3 And/or 0 to 5% of Li 2 O, and/or 0-10% RO, and/or 0-10% Ln 2 O 3 And/or 0-1% of clarifying agent, wherein RO is one or more of MgO, CaO, SrO and BaO, and Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
In a further embodiment, the optical glass of the present invention contains one or more of the following 7 types of components:
(1)Nb 2 O 5 /(K 2 O+Na 2 o) is in the range of 4.0 to 9.0;
(2)Na 2 O/TiO 2 the range of (a) is 0.2 to 1.2;
(3)Nb 2 O 5 /(B 2 O 3 +Na 2 o) is in the range of 2.5 to 15.0;
(4)P 2 O 5 /(K 2 O+Na 2 o) is in the range of 1.5 to 10.0;
(5)P 2 O 5 /TiO 2 the range of (A) is 0.9 to 3.0;
(6)TiO 2 /Nb 2 O 5 the range of (a) is 0.22 to 0.6;
(7)(P 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) The range of (A) is 0.25 to 0.75.
In another embodiment, the optical glass of the present invention contains 20 to 30% by weight of P, based on the total weight of the components in the optical glass 2 O 5 And/or 1-15% of Na 2 O and/or 12 to 20% of TiO 2 And/or 40 to 50% Nb 2 O 5 And/or 0 to 4% SiO 2 And/or 0 to 5% of K 2 O and/or 0 to 3% ZrO 2 And/or 0-5% of ZnO, and/or 0-4% of B 2 O 3 And/or 0 to 4% of Al 2 O 3 And/or 0 to 5% of WO 3 And/or 0 to 3% of Li 2 O, and/or 0-5% RO, and/or 0-5% Ln 2 O 3 And/or 0-0.5% of clarifying agent, wherein RO is one or more of MgO, CaO, SrO and BaO, and Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
In a further embodiment, the optical glass of the present invention contains one or more of the following 7 types of components:
1)Nb 2 O 5 /(K 2 O+Na 2 o) is in the range of 5.0 to 8.0;
2)Na 2 O/TiO 2 the range of (A) is 0.3 to 1.0;
3)Nb 2 O 5 /(B 2 O 3 +Na 2 o) is in the range of 3.5 to 10.0;
4)P 2 O 5 /(K 2 O+Na 2 o) ranges from 2.0 to 9.0;
5)P 2 O 5 /TiO 2 the range of (1) to (2.5);
6)TiO 2 /Nb 2 O 5 the range of (A) is 0.25 to 0.5;
7)(P 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) The range of (A) is 0.3 to 0.6.
In still another embodiment, the optical glass of the present invention contains 23 to 29% by weight of P based on the total weight of the components in the optical glass 2 O 5 And/or 3-9.5% of Na 2 O and/or 13-19% TiO 2 And/or 43 to 50% of Nb 2 O 5 And/or 0-2% SiO 2 And/or 0 to 2% of K 2 O and/or 0 to 2% of ZrO 2 And/or 0-3% of ZnO and/or 0-2% of B 2 O 3 And/or 0 to 3% of Al 2 O 3 And/or 0 to 3% of WO 3 And/or 0 to 1% of Li 2 O, and/or 0-3% RO, and/or 0-3% Ln 2 O 3 And/or 0 to 1% of Sb 2 O 3 Wherein RO is one or more of MgO, CaO, SrO and BaO, Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 One or more of (a).
In a further embodiment, the optical glass of the present invention contains one or more than one of the following 6 cases:
1)Na 2 O/TiO 2 the range of (A) is 0.32 to 0.8;
2)Nb 2 O 5 /(B 2 O 3 +Na 2 o) is in the range of 4.5 to 9.0;
3)P 2 O 5 /(K 2 O+Na 2 o) ranges from 3.2 to 6.75;
4)P 2 O 5 /TiO 2 the range of (1) is 1.2 to 1.8;
5)TiO 2 /Nb 2 O 5 the range of (A) is 0.25 to 0.4;
6)(P 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) The range of (A) is 0.37 to 0.55.
In a specific embodiment, the light of the present inventionThe refractive index (nd) of the optical glass is 1.92 to 1.98, preferably 1.93 to 1.98, and more preferably 1.94 to 1.97. In a specific embodiment, the Abbe number (vd) of the optical glass of the present invention is 15 to 20, preferably 16 to 19. In a specific embodiment, the optical glass of the present invention has a glass transition temperature (T) g ) Is 700 ℃ or lower, preferably 690 ℃ or lower, and more preferably 680 ℃ or lower. In a specific embodiment, the optical glass of the present invention has a density (. rho.) of 3.7g/cm 3 Hereinafter, it is preferably 3.6g/cm 3 Hereinafter, more preferably 3.55g/cm 3 The following. In one particular embodiment, the optical glass of the invention has a stability to water action (D) w ) Is 2 or more, preferably 1. In a particular embodiment, the stability to acid action of the optical glasses according to the invention (D) A ) Is 2 or more, preferably 1. In a specific embodiment, the optical glass of the present invention has a coefficient of thermal expansion (. alpha.) of -30～70℃ ) Is 70X 10 -7 Preferably 65X 10 or less,/K -7 A value of less than or equal to K, more preferably 60X 10 -7 and/K is less than or equal to. In a specific embodiment, the optical glass of the present invention has an upper crystallization limit temperature of 1200 ℃ or lower, preferably 1180 ℃ or lower, and more preferably 1170 ℃ or lower. In a specific embodiment, the optical glass of the present invention has a bubble degree of B class or more, preferably a class or more, and more preferably a class a 0 More than grade. In a specific embodiment, the optical glass of the present invention has an elastic modulus (E) of 9000X 10 7 Pa or more, preferably 9500X 10 7 Pa or more, more preferably 10000X 10 7 Pa or above.
In a second aspect of the present invention, there is provided an optical preform made of the optical glass of the present invention.
In a third aspect of the present invention, there is provided an optical element made of the optical glass or optical preform of the present invention.
In a fourth aspect of the present invention, there is provided an optical instrument comprising the above optical glass or optical element.
According to the invention, by adjusting the weight percentage of each component forming the optical glass and adjusting the ratio of each component, the optical glass has high refractive index and high dispersion, and simultaneously has excellent chemical stability and bubble degree.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. In the present specification, the contents of the respective components (ingredients) are all expressed in terms of weight percentage with respect 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 raw materials as the constituent components of the optical glass of the present invention are decomposed and converted to oxides when they are melted, the total amount of the oxides is 100%.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include endpoints, 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 only A, or only B, or both A and B.
[ essential Components and optional Components ]
In the present invention, P 2 O 5 Is a skeleton component of a phosphate formula system, and mainly has the functions of reducing the melting temperature of glass and improving the thermal stability and light transmittance of the glass. When P is present 2 O 5 When the content is more than 35%, it is difficult to obtain high refractive index and high dispersion properties; when P is 2 O 5 When the content is less than 15%, the melting temperature of the optical glass is high and the transmittance of the glass is poor. Accordingly, in the optical glass of the present invention, P 2 O 5 The lower limit of the content range is 15%, preferably 20%, more preferably 23%; p 2 O 5 The upper limit of the content range is 35%, preferably 30%, more preferably 29%.
Nb 2 O 5 Is an essential component for imparting high-refractivity and high-dispersion properties to the optical glass of the present invention,and simultaneously, the chemical stability and the devitrification resistance of the optical glass can be improved. When Nb 2 O 5 When the content of (b) is less than 38%, high refractive index and high dispersion properties cannot be obtained; when Nb is 2 O 5 When the content exceeds 52%, the devitrification resistance of the glass is lowered and the chemical stability is deteriorated. Therefore, in the optical glass of the present invention, Nb 2 O 5 The lower limit of the content range is 38%, preferably 40%, more preferably 43%, and the upper limit of the content range is 52%, preferably 50%.
Na 2 O and K 2 O can lower the glass transition temperature (T) g ) And the melting performance of the glass is improved. However, the content of the alkali metal oxide is too large, so that the refractive index is lowered and it is difficult to obtain desired optical properties; when the content is too small, the glass has poor melting properties and a transition temperature (T) g ) Higher. In the invention, Na with the total content of 1-18% is introduced 2 O and K 2 O to obtain the above properties.
The inventor discovers that when Nb is used 2 O 5 /(K 2 O+Na 2 O) value exceeding 10.0, the chemical stability of the glass is lowered, and Nb is added 2 O 5 /(K 2 O+Na 2 O) value less than 2.0, it is difficult for the glass to obtain high-refractivity and high-dispersion properties, so Nb in the present invention 2 O 5 /(K 2 O+Na 2 O) has a value of 2.0 to 10.0, and in some embodiments, it is preferred when Nb 2 O 5 /(K 2 O+Na 2 O) value of 4.0 to 9.0, the glass bubble content can be increased, and Nb is more preferable 2 O 5 /(K 2 O+Na 2 O) is 5.0 to 8.0.
In some embodiments, when P 2 O 5 /(K 2 O+Na 2 O) of more than 10.0, the optical glass has poor melting property and a transition temperature (T) g ) High, when P is 2 O 5 /(K 2 O+Na 2 O) less than 1.5, the optical glass is liable to blister. Thus, P 2 O 5 /(K 2 O+Na 2 O) is in the range of 1.5 to 10.0, preferably 2.0 to 9.0, more preferably 3.20 to 6.75The optical glass has excellent bubble degree and lower transition temperature (T) g )。
However, the alkali metal oxides have different effects in the present invention and thus have different contents.
Na 2 O lowers the transition temperature of the glass and improves the melting property of the glass, and when the content thereof is less than 1%, the above effects are difficult to achieve, and when the content thereof is more than 15%, the refractive index of the glass decreases, and it is difficult to obtain the high refractive index required by the present invention. Thus Na in this application 2 The content of O is 1 to 15%, preferably 2 to 10%, more preferably 3 to 9.5%.
K 2 O can improve the stability and melting property of the glass, but when the content exceeds 5%, the devitrification resistance of the glass is lowered and the refractive index is lowered, so that K in the present application 2 The content of O is 0 to 5%, preferably 0 to 3%, more preferably 0 to 2%.
TiO 2 The effect of (a) is to increase the chemical stability of the glass, while increasing the refractive index and dispersion value of the glass. When TiO is present 2 When the content of (b) exceeds 25%, the devitrification resistance of the optical glass is lowered and the glass is colored, resulting in lowering the transmittance of the glass in the visible light region; when TiO is in the glass 2 When the content of (A) is less than 10%, the requirement of the optical glass in terms of chemical stability cannot be satisfied. Therefore, in the optical glass of the present invention, TiO 2 The lower limit of the content range is 10%, preferably 12%, more preferably 13%, TiO 2 The upper limit of the content range is 25%, preferably 20%, more preferably 19%.
In some embodiments, by controlling Na 2 O/TiO 2 The range of (A) is 0.2-1.2, the glass can obtain proper high-temperature viscosity, is easy to process and produce, and reduces the thermal expansion coefficient and the transformation temperature (T) of the optical glass g ). Preferably Na 2 O/TiO 2 In the range of 0.3 to 1.0, more preferably Na 2 O/TiO 2 The range of (A) is 0.32 to 0.8. Na (Na) 2 O/TiO 2 Within the above range, has a low T g The optical glass has high refractive index and high dispersion, and can be heated at a lower temperatureAnd the reaction degree of the precision glass mold with the mold during molding can be reduced, and the service life of the mold can be prolonged.
In some embodiments, if P 2 O 5 /TiO 2 If the glass content is more than 3.0, the optical glass has a low elastic modulus and a poor deformation resistance. If P is 2 O 5 /TiO 2 When the thermal expansion coefficient is less than 0.9, the optical glass has a high thermal expansion coefficient and is easily deformed at high temperatures. By controlling P 2 O 5 /TiO 2 The range of (A) is 0.9 to 3.0, which can increase the elastic modulus of the optical glass and reduce the thermal expansion coefficient of the glass, preferably 1.0 to 2.5, more preferably 1.2 to 1.8.
In some embodiments, by controlling TiO 2 /Nb 2 O 5 The range of (A) is within 0.22-0.60, so that the optical glass can achieve low density while obtaining high refraction and high dispersion. Preferably TiO 2 /Nb 2 O 5 The range of (A) is 0.25 to 0.50, more preferably 0.25 to 0.40.
SiO 2 Is a component for reducing glass coloration, improving the transmittance to short-wavelength visible light, promoting the formation of stable glass, and improving the devitrification resistance of glass in optical glass, but when SiO 2 When the content of (B) exceeds 5%, the glass tends to be refractory. Therefore, in the optical glass of the present invention, SiO 2 The upper limit of the content range is 5%, preferably 4%, more preferably 2%.
In some embodiments, when (P) 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) When it exceeds 0.75, the elastic modulus of the optical glass decreases, when (P) 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) When the amount is less than 0.25, the glass forming stability and chemical stability of the optical glass are lowered. Thus (P) 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) The range of (A) is 0.25 to 0.75, preferably 0.3 to 0.6, more preferably 0.37 to 0.55, and the optical glass has a high elastic modulus, excellent glass forming stability and good chemical stability.
In some casesIn the embodiment, the optical glass of the present invention is prepared by making the optical glass contain SiO as a component 2 /TiO 2 When the content is more than 0 to 0.3, the optical glass has higher elastic modulus and excellent devitrification resistance, and SiO is preferred 2 /TiO 2 Is 0.01 to 0.25, preferably 0.01 to 0.1.
ZrO 2 The component is an optional component in the optical glass of the present invention, and is a component for reducing coloring, improving transmittance to short-wavelength visible light, promoting formation of stable glass, and improving resistance to devitrification of glass. By making ZrO 2 The content of the component (A) is 5% or less, and ZrO can be inhibited 2 The refractive index decreases due to the component, and a desired high refractive index is easily obtained. Thus, in the optical glass of the present invention, ZrO 2 The upper limit of the content range is 5%, preferably 3%, more preferably 2%. ZrO (ZrO) 2 The lower limit of the content range may be zero.
ZnO, which improves the refractive index of the glass, improves the glass stability, meltability, press-formability and lowers the glass transition temperature, is an optional component in the optical glass of the present invention. By setting the content of the ZnO component to 8% or less, a desired high refractive index and a desired high dispersion value can be easily obtained. Therefore, in the optical glass of the present invention, the upper limit of the ZnO content range is 8%, preferably 5%, and more preferably 3%. The lower limit of the range of the ZnO content may be zero.
B 2 O 3 The component forms a glass network and improves the devitrification resistance of the glass, but when the content exceeds 5%, the refractive index and dispersion value of the glass are lowered. Thus, in the optical glass of the present invention, B 2 O 3 The upper limit of the content range is 5%, preferably 4%, more preferably 2%.
In some embodiments, if Nb 2 O 5 /(B 2 O 3 +Na 2 O) of more than 15.0, the optical glass has poor melting property and a transition temperature (T) g ) Is higher. If Nb 2 O 5 /(B 2 O 3 +Na 2 O) is less than 2.5, the optical glass is easy to crystallize, and the finished glass has more bubbles. Let Nb 2 O 5 /(B 2 O 3 +Na 2 O) is in the range of 2.5 to 15.0, preferably 3.5 to 10.0, more preferably 4.5 to 9.0, and the optical glass has good meltability, excellent devitrification resistance and a bubble degree.
Al 2 O 3 Is a component for improving the chemical stability of the glass and increasing the viscosity of the glass when it is melted, and is an optional component in the optical glass of the present invention. By making Al 2 O 3 The content of the component (A) is 6% or less, and the meltability of the glass can be improved and the devitrification tendency of the glass can be reduced. Therefore, in the optical glass of the present invention, Al 2 O 3 The upper limit of the content range is 6%, preferably 4%, more preferably 3%. Al (Al) 2 O 3 The lower limit of the content range may be zero.
WO 3 Is a component for increasing the refractive index of the glass and increasing the dispersion value of the glass, and is an optional component in the optical glass of the present invention. By reacting WO 3 The content of the component (A) is 8% or less, and the transmittance of the glass to short-wavelength visible light can be suppressed, and a desired high refractive index and a desired high dispersion value can be easily obtained. Therefore, in the optical glass of the present invention, WO 3 The upper limit of the content range is 8%, preferably 5%, more preferably 3%. WO 3 The lower limit of the content range may be zero.
Li 2 O is a component for increasing the melting property of the glass and lowering the glass transition temperature, and is an optional component in the optical glass of the present invention. By reacting Li 2 The content of the O component is 5% or less, and the desired high refractive index can be easily obtained, and the crystallization upper limit temperature of the glass can be lowered to improve the stability of the glass. Therefore, in the optical glass of the present invention, Li 2 The upper limit of the O content range is 5%, preferably 3%, more preferably 1%. Li 2 The lower limit of the O content range may be zero.
RO (i.e., one or more of MgO, CaO, SrO, and BaO) is a component that lowers the devitrification temperature of the glass and improves the resistance of the glass to devitrification, and is an optional component in the optical glass of the present invention. By controlling the RO content to 10% or less, the glass can be inhibited from suffering devitrification resistance and chemical stability. Therefore, in the optical glass of the present invention, the upper limit of the RO content range is 10%, preferably 5%, and more preferably 3%.
Ln 2 O 3 Is a component for increasing the refractive index of the glass and improving the chemical stability of the glass, is an optional component in the optical glass of the present invention, 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 (a). By mixing Ln 2 O 3 The content of (2) is controlled to 10% or less, and the devitrification resistance of the glass can be improved. Thus, in the optical glass of the present invention, Ln 2 O 3 The upper limit of the content range is 10%, preferably 5%, more preferably 3%.
By adding 0-1% of Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more components of the glass refining agent can be used as a refining agent to improve the refining effect of the glass. But when 8b 2 O 3 When the content exceeds 1%, the glass tends to have a reduced fining property and the deterioration of the forming mold is promoted by the strong oxidation thereof, so that Sb in the present invention is 2 O 3 The amount of (B) is 1% or less, preferably 0.5% or less. SnO 2 SnO may be added as a fining agent, but when the content exceeds 1%, the glass is colored, or when the glass is heated, softened and press-molded again, Sn tends to become a starting point of nucleation and devitrification occurs, so that the SnO of the present invention 2 And SnO are contained in an amount of 1% or less, preferably 0.5% or less, and more preferably not added. CeO (CeO) 2 Action and addition amount ratio of (B) and SnO 2 The content is 1% or less, preferably 0.5% or less, and more preferably no additive.
[ regarding components that should not be contained ]
If necessary, other components not mentioned above can be added within a range not impairing the characteristics of the glass of the present invention. However, since the glass is colored and absorbs at a specific wavelength in the visible light region even when a small amount of a transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained alone or in combination, thereby reducing the property of the present invention to improve the effect of the visible light transmittance, it is preferable that the optical glass, which requires transmittance at a wavelength in the visible light region, is not substantially contained.
Cations of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in recent years, 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.
In order to achieve environmental friendliness, the optical glass of the present invention does not contain As 2 O 3 And PbO. Although As 2 O 3 Has the effects of eliminating bubbles and better preventing the glass from coloring, but As 2 O 3 The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As 2 O 3 All cause environmental pollution.
The glass of the invention is produced by adopting conventional raw materials and conventional processes, and phosphoric acid, metaphosphate, pyrophosphate or phosphorus pentoxide is used as P 2 O 5 The raw materials are carbonate, nitrate, sulfate, oxide and the like as other component raw materials. After the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1200-1280 ℃ for smelting, and after clarification and sufficient homogenization, casting or leaking injection molding is carried out at 1150-1200 ℃ to obtain the optical glass. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
The performance parameters of the optical glass of the present invention were measured in the following manner.
[ refractive index and Abbe number ]
Refractive index (n) d ) And Abbe number (v) d ) Testing according to GB/T7962.1-2010.
Refractive index (n) of the optical glass of the present invention d ) 1.92-1.98, preferably 1.93-1.98, more preferably 1.94-1.97; abbe number (v) of the optical glass of the present invention d ) 15 to 20, preferably 16 to 19.
[ transition temperature ]
Transition temperature (T) g ) Testing according to GB/T7962.16-2010.
Glass transition temperature (T) of the optical glass of the present invention g ) Is 700 ℃ or lower, preferably 690 ℃ or lower, and more preferably 680 ℃ or lower.
[ Density ]
The density (. rho.) was tested in accordance with GB/T7962.20-2010.
The optical glass of the present invention has a density (. rho.) of 3.7g/cm 3 Hereinafter, it is preferably 3.6g/cm 3 Hereinafter, more preferably 3.55g/cm 3 The following.
[ chemical stability ]
Chemical stability in the present invention includes water-resistant stability (D) w ) And stability against acid action (D) A ) It was tested according to GB/T17129.
Stability to Water of the optical glass of the present invention (D) W ) Is 2 or more, preferably 1; stability against acid action of the optical glass of the present invention (D) A ) Is 2 or more, preferably 1.
[ coefficient of thermal expansion ]
Coefficient of thermal expansion (alpha) -30～70℃ ) Testing according to GB/T7962.16-2010.
The coefficient of thermal expansion (. alpha.) of the optical glass of the present invention -30～70℃ ) Is 70X 10 -7 Preferably 65X 10 or less,/K -7 A value of less than or equal to K, more preferably 60X 10 -7 and/K is less than or equal to.
[ degree of bubbling ]
The bubble degree was tested according to GB/T7962.8-2010.
The optical glass of the present invention has a bubble degree of B class or more, preferably A class or more, more preferably A class 0 Stage byThe above.
[ upper limit temperature of crystallization ]
Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.
The upper limit temperature of crystallization of the optical glass of the present invention is 1200 ℃ or lower, preferably 1180 ℃ or lower, and more preferably 1170 ℃ or lower.
[ modulus of elasticity ]
The elastic modulus is expressed as Young's modulus and is measured as follows: 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.
Wherein the content of the first and second substances,
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 。
The elastic modulus (E) of the optical glass of the present invention is 9000X 10 7 Pa or more, preferably 9500X 10 7 Pa or more, more preferably 10000X 10 7 Pa or above.
The present invention also provides an optical preform made of the optical glass of the present invention, an optical element made of the optical glass or the optical preform of the present invention, and an optical instrument comprising the above optical glass or the optical element.
The invention can make the optical glass have excellent chemical stability and bubble degree on the premise of easily obtaining expected refractive index and Abbe number by adjusting the weight percentage of each component forming the optical glass and adjusting the ratio of each component. Meanwhile, the optical glass provided by the invention also has excellent transition temperature, so that the optical glass can be processed and molded at lower temperature, and the finished optical glass has the characteristics of better chemical stability, low expansion rate and the like, so as to meet the application of the optical glass in the field of photoelectrons.
The optical preform and the optical element of the present invention are each formed of the above-described optical glass of the present invention. The optical preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of 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.
Further, since the prism has a relatively high refractive index, by combining the prism with an imaging optical system and bending the optical path to a desired direction, a compact and wide-angle optical system can be realized.
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like.
The present invention is described in detail below with reference to various embodiments.
In the following examples and comparative examples, optical glasses were produced as follows:
weighing raw materials corresponding to all optical glass components in proportion, fully mixing, adding into a platinum crucible, melting, clarifying, homogenizing and cooling at 1200-1280 ℃; pouring the molten glass into the preheated metal mold at the temperature of 1150-1200 ℃; the molten glass and the metal mold are placed in an annealing furnace together, and the optical glass is obtained after slow cooling annealing. The various performance parameters of the optical glass were measured according to the measurement methods described hereinbefore.
The compositions of the optical glasses of examples 1 to 40 and comparative examples 1 to 6 are shown in tables 1 and 2 below, respectively; the corresponding properties of the optical glasses of examples 1 to 40 and comparative examples 1 to 6 are shown in tables 3 and 4, respectively.
Table 1: compositions of optical glasses of examples 1 to 40
Table 1 (next): compositions of optical glasses of examples 1 to 40
Table 1 (next): compositions of optical glasses of examples 1 to 40
Table 2: compositions of optical glasses of comparative examples 1 to 6
Table 3: optical glass Properties of examples 1 to 40
Table 3 (next): optical glass Properties of examples 1 to 40
Table 4: optical glass Properties of comparative examples 1 to 6
As can be seen from the above tables 1 and 3, when the weight percentages of the components and the ratios between the components in the optical glass are within the ranges of the present invention, the optical glass having high refractive index, high dispersion and other optical constants, as well as good chemical stability and degree of foaming can be produced. Moreover, the optical glass of the present invention is remarkably improved in optical properties, workability, glass forming stability, chemical stability, low density, deformation resistance, crystallization resistance, and low blister degree.
When the weight percentage of each component in the optical glass and the ratio of each component are in the range, the optical glass can be processed and molded at lower temperature while having optical constants such as refractive index, Abbe number and the like, and the finished optical glass has the characteristics of better chemical stability, low expansion rate and the like so as to meet the application of the optical glass in the field of photoelectrons.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The optical glass is characterized in that the component content of the optical glass is expressed by weight percent and contains 15-35 percent of P 2 O 5 1 to 18% of Na 2 O+K 2 O, 10-25% of TiO 2 And 38-52% of Nb 2 O 5 Wherein Nb 2 O 5 /(K 2 O+Na 2 O) is in the range of 2.87 to 10.0.
2. An optical glass according to claim 1, characterized in that it further comprises 0-5% by weight of SiO 2 And/or 0 to 5% of ZrO 2 And/or 0-8% of ZnO and/or 0-5% of B 2 O 3 And/or 0 to 6% of Al 2 O 3 And/or 0 to 8% of WO 3 And/or 0 to 5% of Li 2 O, and/or 0 to 10% RO, and/or 0-10% Ln 2 O 3 And/or 0-1% of clarifying agent, wherein RO is one or more of MgO, CaO, SrO and BaO, and Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The clarifying agent is Sb 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
3. The optical glass according to claim 1 or 2, wherein the content of the optical glass component satisfies one or more of the following 7 cases:
1)Nb 2 O 5 /(K 2 O+Na 2 o) is in the range of 4.0 to 9.0, and Nb is preferable 2 O 5 /(K 2 O+Na 2 O) is in the range of 5.0 to 8.0;
2)Na 2 O/TiO 2 in the range of 0.2 to 1.2, preferably Na 2 O/TiO 2 In the range of 0.3 to 1.0, more preferably Na 2 O/TiO 2 The range of (A) is 0.32 to 0.8;
3)Nb 2 O 5 /(B 2 O 3 +Na 2 o) is in the range of 2.5 to 15.0, and Nb is preferable 2 O 5 /(B 2 O 3 +Na 2 O) is in the range of 3.5 to 10.0, and Nb is more preferable 2 O 5 /(B 2 O 3 +Na 2 O) is in the range of 4.5 to 9.0;
4)P 2 O 5 /(K 2 O+Na 2 o) is in the range of 1.5 to 10.0, preferably P 2 O 5 /(K 2 O+Na 2 O) is in the range of 2.0 to 9.0, more preferably P 2 O 5 /(K 2 O+Na 2 O) ranges from 3.2 to 6.75;
5)P 2 O 5 /TiO 2 in the range of 0.9 to 3.0, preferably P 2 O 5 /TiO 2 In the range of 1.0 to 2.5, more preferably P 2 O 5 /TiO 2 The range of (1) is 1.2 to 1.8;
6)TiO 2 /Nb 2 O 5 in the range of 0.22 to 06, preferably TiO 2 /Nb 2 O 5 In the range of 0.25 to 0.5, more preferably TiO 2 /Nb 2 O 5 The range of (A) is 0.25 to 0.4;
7)(P 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) Is in the range of 0.25 to 0.75, preferably (P) 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) Is in the range of 0.3 to 0.6, more preferably (P) 2 O 5 +SiO 2 )/(TiO 2 +Nb 2 O 5 ) The range of (A) is 0.37 to 0.55.
4. An optical glass according to claim 1 or 2, wherein the component content of the optical glass is, in weight percent, 20 to 30% of P 2 O 5 And/or 1-15% of Na 2 O and/or 12 to 20% of TiO 2 And/or 40-50% of Nb 2 O 5 And/or 0 to 4% SiO 2 And/or 0-5% of K 2 O and/or 0 to 3% ZrO 2 And/or 0-5% of ZnO, and/or 0-4% of B 2 O 3 And/or 0 to 4% of Al 2 O 3 And/or 0 to 5% of WO 3 And/or 0 to 3% of Li 2 O, and/or 0-5% RO, and/or 0-5% Ln 2 O 3 And/or 0-0.5% of clarifying agent, wherein RO is one or more of MgO, CaO, SrO and BaO, and Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
5. An optical glass according to claim 1 or 2, characterized in that the component content in the optical glass expressed by weight percentage comprises 23-29% of P 2 O 5 And/or 3-9.5% of Na 2 O and/or 13-19% TiO 2 And/or 43 to 50% of Nb 2 O 5 And/or 0-2% SiO 2 And/or 0 to 2% of K 2 O and/or 0 to 2% of ZrO 2 And/or 0-3% of ZnO and/or 0-2% of B 2 O 3 And/or 0 to 3% of Al 2 O 3 And/or 0 to 3% of WO 3 And/or 0 to 1% of Li 2 O, and/or 0-3% RO, and/or 0-3% Ln 2 O 3 And/or 0 to 1% of Sb 2 O 3 Wherein RO is one or more of MgO, CaO, SrO and BaO, Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 One or more of (a).
6. Optical glass according to claim 1 or 2, characterised in that the refractive index n of the optical glass is d 1.92 to 1.98, preferably 1.93 to 1.98, more preferably 1.94 to 1.97; abbe number v d 15 to 20, preferably 16 to 19.
7. An optical glass according to claim 1 or 2, characterised in that the glass transition temperature T of the optical glass is g 700 ℃ or lower, preferably 690 ℃ or lower, more preferably 680 ℃ or lower; and/or a density rho of 3.7g/cm 3 Hereinafter, it is preferably 3.6g/cm 3 Hereinafter, more preferably 3.55g/cm 3 The following; and/or stability against water action D W Is 2 or more, preferably 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or coefficient of thermal expansion alpha -30～70℃ Is 70X 10 -7 Preferably 65X 10 or less,/K -7 A value of not more than K, more preferably 60X 10 -7 below/K; and/or the upper limit temperature of crystallization is 1200 ℃ or lower, preferably 1180 ℃ or lower, more preferably 1170 ℃ or lower; and/or a degree of bubbling of B class or more, preferably A class or more, more preferably A 0 More than grade; and/or an elastic modulus E of 9000X 10 7 Pa or more, preferably 9500X 10 7 Pa or more, more preferably 10000X 10 7 Pa or above.
8. An optical preform, characterized by being made of the optical glass according to any one of claims 1 to 7.
9. An optical element made of the optical glass according to any one of claims 1 to 7 or the optical preform according to claim 8.
10. An optical device comprising the optical glass according to any one of claims 1 to 7 or the optical element according to claim 9.
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| CN114644454B (en) * | 2020-12-18 | 2023-07-18 | 成都光明光电股份有限公司 | Optical glass, optical element and optical instrument |
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Application publication date: 20220805 |