CN116573849A - Optical filter glass, preparation method thereof and optical element - Google Patents
Optical filter glass, preparation method thereof and optical element Download PDFInfo
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- CN116573849A CN116573849A CN202310407900.7A CN202310407900A CN116573849A CN 116573849 A CN116573849 A CN 116573849A CN 202310407900 A CN202310407900 A CN 202310407900A CN 116573849 A CN116573849 A CN 116573849A
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- 239000011521 glass Substances 0.000 title claims abstract description 198
- 230000003287 optical effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 12
- 238000002834 transmittance Methods 0.000 claims abstract description 35
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000006060 molten glass Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 239000002096 quantum dot Substances 0.000 description 26
- 239000011669 selenium Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 15
- 238000013461 design Methods 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910004613 CdTe Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 229910007709 ZnTe Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 etc.) Chemical compound 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- AUQMGYLQQPSCNH-UHFFFAOYSA-L NIR-2 dye Chemical compound [K+].[K+].C1=CC2=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C=C2C(C2(C)C)=C1[N+](CC)=C2C=CC=CC=C1C(C)(C)C2=CC(C(O)=O)=CC=C2N1CCCCS([O-])(=O)=O AUQMGYLQQPSCNH-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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 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
- 238000005381 potential energy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
-
- 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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/226—Glass filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a filter glassGlass, a method for producing the same and an optical element. The filter glass comprises the following components in percentage by weight: siO (SiO) 2 ：30％～70％；B 2 O 3 ：3％～20％；ZnO：8～30％；CdS：1～10％；Se：0.4～5％；Te：0.5～5％；Al 2 O 3 ：0～3％；Li 2 O、Na 2 O、K 2 Sum of O contents Li 2 O+Na 2 O+K 2 O is 5% -28%; the sum of the contents of MgO, caO, baO and SrO is 0 to 8 percent of MgO+CaO+BaO+SrO. The filter glass has relatively low production cost, relatively controllable ultraviolet and visible light cut-off in the process of crystal formation and very high transmittance at the near infrared end.
Description
Technical Field
The invention relates to filter glass, a preparation method thereof and an optical element, and belongs to the field of filter glass.
Background
In recent years, with the development of the photoelectric industry, the near infrared band detection has been increasingly applied, and especially in intelligent technologies and equipment such as unmanned, the near infrared laser is utilized to sense the surrounding environment in real time, so that decisions are provided for the actions and movements of the intelligent equipment. In order to accurately sense the external environment, it is required that the optical system has high near infrared transmittance while being capable of well filtering out ultraviolet light and visible light. Among the current ways in the glass industry to achieve this function well are glass coating and glass tinting.
Compared with glass coloring, the coating technology has higher difficulty and higher cost, and the film layer can possibly interfere with imaging optical signals. In glass coloring, ion-colored glass has the properties of discontinuous light absorption and transmission wave bands, low transmittance, complex preparation process of colloid-colored glass, high cost and low cut-off degree, and the two types of glass can not provide accurate external reality for an optical system, while semiconductor quantum dot glass, especially CdSe-CdTe quantum dot glass, can realize cut-off of ultraviolet light and visible light and high transmission of near infrared region.
Patent CN105293906A publicThe CdTe quantum dot doped glass and the preparation method thereof have the advantages that the cost of the raw material ZnTe for forming the quantum dots is high, the raw material ZnTe is easy to oxidize in the high-temperature smelting process, and CdTe quantum dot crystals are difficult to form in the glass. Patent CN111662008A discloses a high-transmittance Sb with ultraviolet and visible light cut-off and near infrared 2 Se 3 Quantum dot glass and preparation method thereof, and Sb 2 Se 3 The potential energy of quantum dot formation is larger, and the difficulty of crystal formation is larger.
Therefore, research on cut-off type optical filter glass with relatively low production cost, relatively controllable crystal formation process, ultraviolet and visible light cut-off and high near infrared transmission and a preparation method thereof become technical problems to be solved urgently.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the invention firstly provides the filter glass with relatively low production cost, relatively controllable ultraviolet and visible light cut-off and near infrared high transmission in the crystal forming process.
Furthermore, the invention also provides a preparation method of the filter glass, which is simple and easy to implement, raw materials are easy to obtain, and the preparation method is suitable for mass production.
Solution for solving the problem
The invention provides filter glass which comprises the following components in percentage by weight:
SiO 2 :30% -70%, preferably 35% -68%, more preferably 38% -65%;
B 2 O 3 :3% -20%, preferably 4% -15%, more preferably 5% -10%;
ZnO:8 to 30%, preferably 10 to 28%, more preferably 12 to 25%;
CdS:1 to 10%, preferably 2 to 8%, more preferably 2 to 6%;
se:0.4 to 5%, preferably 0.7 to 4%, more preferably 0.8 to 3.5%;
te:0.5 to 5%, preferably 0.7 to 4%, more preferably 0.8 to 3%;
Al 2 O 3 :0 to 3%, preferably 0 to 2%, more preferably 0 to 1%;
Li 2 O、Na 2 O、K 2 sum of O contents Li 2 O+Na 2 O+K 2 O is 5% -28%, preferably 7% -23%, more preferably 9% -20%;
the sum of MgO, caO, baO and SrO content is MgO+CaO+BaO+SrO 0 to 8%, preferably 0 to 6%, more preferably 0 to 4%.
The filter glass according to the invention, wherein, in weight percent, li 2 The O content is 0 to 3%, preferably 0 to 1%, more preferably not incorporated; na (Na) 2 The content of O is 2 to 9%, preferably 3 to 8%, more preferably 4 to 8%; k (K) 2 The content of O is 3 to 16%, preferably 4 to 14%, more preferably 5 to 12%; and/or the number of the groups of groups,
the content of MgO in the filter glass is 0-2%, preferably 0-1.5%, more preferably 0-1% by weight; the CaO content is 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%; the SrO content is 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%; the BaO content is 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%.
The filter glass according to the invention, wherein SiO is in weight percent 2 And Al 2 O 3 Sum of the contents of (B) and B 2 O 3 、Li 2 O、Na 2 O and K 2 Ratio of sum of O contents Sigma (SiO) 2 +Al 2 O 3 )/∑(B 2 O 3 +Li 2 O+Na 2 O+K 2 O) is 0.5 to 3.0, preferably 0.8 to 2.5, more preferably 1 to 2.2.
The filter glass of the invention comprises ZnO and SiO in percentage by weight 2 Ratio ZnO/SiO 2 From 0.1 to 1, preferably from 0.2 to 0.8, more preferably from 0.3 to 0.7.
The filter glass according to the present invention, wherein the ratio Se/Te of Se to Te content is less than 2.0, preferably less than 1.5, more preferably less than 1, in weight percent.
The filter glass according to the invention, wherein the ratio of sum of Se and Te content to CdS, sigma (Se+Te)/CdS, in weight percent, is greater than 0.05, preferably greater than 0.1, more preferably sigma (Se+Te)/CdS is greater than 0.2.
The filter glass according to the present invention, wherein the cutoff wavelength of the filter glass is 600nm or more when the thickness of the filter glass is 2 mm;
when the thickness of the filter glass is 2mm, the transmittance of 850-900 nm is more than 80%, the transmittance of 900-950 nm is more than 85%, and the transmittance of 950-2000 nm is more than 88%.
The filter glass of the invention, wherein the acid resistance of the filter glass is more than 3 types; the water resistance of the filter glass is more than 3 types;
the Young's modulus of the filter glass is more than 61 GPa;
expansion coefficient alpha of the filter glass 20-300℃ 80X 10 -7 and/K.
The invention also provides a preparation method of the optical filter glass, which comprises the following steps:
uniformly mixing the raw materials of all the components of the glass according to a proportion, and putting the mixture into a melting furnace at 1200-1400 ℃ for melting to form molten glass;
homogenizing the molten glass to eliminate bubbles in the glass;
casting or leaking homogenized molten glass into a mold for molding to obtain a molded body;
and (3) placing the formed body into an annealing furnace, preserving heat for 24-72h at 550-700 ℃ to carry out nucleation reaction on the glass, and preserving heat for 12-72h at 550-700 ℃ to enable crystals in the glass to grow up to obtain the filter glass.
The invention also provides an optical element comprising the filter glass according to the invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The filter glass has relatively low production cost, relatively controllable ultraviolet and visible light cut-off in the process of crystal formation and very high transmittance at the near infrared end.
Furthermore, the preparation method of the filter glass is simple and feasible, raw materials are easy to obtain, and the filter glass is suitable for mass production.
Drawings
FIG. 1 is a graph of spectral transmittance of glass according to example 1 of the present invention.
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
The term "not containing" 0% "as used herein means that the compound, element or the like is not intentionally added to the glass of the present invention as a raw material, but that some impurities or components other than intentionally added may be present as a raw material and/or equipment for producing the glass, and that the impurities or components are contained in a small amount or a trace amount in the final glass, which is also within the scope of the present invention.
The invention firstly provides filter glass which comprises the following components in percentage by weight:
SiO 2 :30% -70%, preferably 35% -68%, more preferably 38% -65%;
B 2 O 3 :3% -20%, preferably 4% -15%, more preferably 5% -10%;
ZnO:8 to 30%, preferably 10 to 28%, more preferably 12 to 25%;
CdS:1 to 10%, preferably 2 to 8%, more preferably 2 to 6%;
se:0.4 to 5%, preferably 0.7 to 4%, more preferably 0.8 to 3.5%;
te:0.5 to 5%, preferably 0.7 to 4%, more preferably 0.8 to 3%;
Al 2 O 3 :0 to 3%, preferably 0 to 2%, more preferably 0 to 1%;
Li 2 O、Na 2 O、K 2 sum of O contents Li 2 O+Na 2 O+K 2 O is 5% -28%, preferably 7% -23%, more preferably 9% -20%;
the sum of the contents of MgO, caO, baO and SrO is MgO+CaO+BaO+SrO in the range of 0 to 8%, preferably 0 to 6%, more preferably 0 to 4%.
The filter glass has relatively low production cost, relatively controllable ultraviolet and visible light cut-off in the process of crystal formation and very high transmittance at the near infrared end.
In the system glass of the invention, siO 2 The glass is an important component for forming a proportional framework, and the glass is endowed with good thermal stability, so that the quantum dot components are stably combined in the glass to form crystals, and meanwhile, the glass has good chemical stability, mechanical strength and crystallization performance. If the content is less than 30%, the thermal stability of the glass is poor, the formation of quantum dot crystals is uncontrollable, the cut-off performance cannot meet the design requirement, and meanwhile, the chemical stability and mechanical strength of the glass are poor; if the content is higher than 70%, the glass melting process temperature is high, the volatilization of the quantum dot components is serious, and the cut-off performance of the glass is reduced. Thus SiO in the composition 2 The content of (2) is 30% to 70%, preferably 35% to 68%, and more preferably 38% to 65%.
Li 2 O、Na 2 O、K 2 Sum of O contents Li 2 O+Na 2 O+K 2 O mainly plays roles of improving glass melting efficiency, reducing high-temperature viscosity of glass, being beneficial to eliminating bubbles, improving dissolution of quantum dot components and the like in the glass. When the content is lower than 5%, the fluxing effect is not obvious, and the expansion performance of the glass is lower than the design standard; if the content is more than 28%, the content of free oxygen in the glass increases, the network structure is destroyed, the crystallization property of the glass decreases, the cut-off property and near infrared transmission of the glass decrease, and the chemical stability and mechanical property of the glass decrease. Thus Li 2 O、Na 2 O、K 2 Sum of O contents Li 2 O+Na 2 O+K 2 The content of O is 5 to 28%, preferably 7 to 23%, and more preferably 9 to 20%.
In some specific embodiments, li 2 The O can effectively reduce the high-temperature viscosity of the glass and the surface tension of the glass, and is helpful for eliminating bubbles in the glass. But Li + The glass has strong aggregation effect, is a crystal nucleus agent, is easy to interfere the conversion of quantum dot components, reduces the cut-off performance of the glass, and simultaneously has Li 2 The cost of O is high and the introduction of glass increases the manufacturing cost. Thus Li in the component 2 The content of O is 0 to 3%, preferably 0 to 1%, and the amount of O is preferably 0 to 1% by weightThe one step is preferably not introduced.
Na 2 The O can improve the glass melting efficiency, reduce the high-temperature viscosity of the glass, help to eliminate bubbles, improve the dissolution of quantum dot components and the like in the glass, and can also improve the near infrared transmittance of the glass and the thermal expansion coefficient of the glass. Na (Na) 2 When the content of O is too low, the near infrared transmittance and the expansion coefficient of the glass do not meet the design requirements, na 2 When the content of O is too high, the chemical stability and crystallization property of the glass are poor. Thus, in the present invention, na 2 The content of O may be 2% to 9%, preferably 3% to 8%, and more preferably 4% to 8%.
In the present invention, na 2 O and K 2 O has a similar effect in glass, furthermore K 2 O increases the steepness of the light absorption curve of the glass. In order to comprehensively ensure the cut-off property, chemical stability, thermal design requirement and mechanical property of the glass, K in the component 2 The content of O is 3% -16%, preferably 4% -14%, and more preferably 5% -12%.
B 2 O 3 The glass belongs to a network intermediate, can accelerate the melting and clarifying processes of the glass, but the too high content can change the structural change of the glass, reduce the solubility of the colorant and the precipitation of the colorant, and lead to the reduction of the glass cut-off performance. Thus B in the component 2 O 3 The content of (2) is 3% to 20%, preferably 4% to 15%, and more preferably 5% to 10%.
Al 2 O 3 The glass is a network intermediate, and can further enter a network framework, so that the glass framework is more compact, and the chemical stability, mechanical property and thermal stability of the glass are improved. However, when the content is higher, the glass smelting difficulty is increased, which is unfavorable for the formation of quantum dot crystals, thus Al in the components 2 O 3 The content of (2) is 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%.
The viscosity of the glass has an important effect on the growth of the quantum dot crystals. SiO in the present invention 2 And Al 2 O 3 Sum of the contents of (B) and B 2 O 3 、Li 2 O、Na 2 O and K 2 Ratio of sum of O contents Sigma (SiO) 2 +Al 2 O 3 )/∑(B 2 O 3 +Li 2 O+Na 2 O+K 2 When O) is too high, the viscosity of the glass is too high, which is unfavorable for the formation and growth of crystals in the process of developing the glass, and the expansion coefficient of the glass does not meet the design requirement, if Sigma (SiO) 2 +Al 2 O 3 )/∑(B 2 O 3 +R 2 If O) is too low, the stability of the glass is poor and the design requirements are not satisfied, so that Sigma (SiO) 2 +Al 2 O 3 )/∑(B 2 O 3 +Li 2 O+Na 2 O+K 2 O) is 0.5 to 3.0, preferably 0.8 to 2.5, and more preferably 1 to 2.2.
ZnO is one of indispensable components in the quantum dot glass, can form more stable zinc compounds with the quantum dot components in the glass smelting process, is favorable for reducing volatilization of quantum dot components and improving the cut-off performance of the glass, but the content is too high, so that the crystallization performance of the glass can be reduced, and the permeability of the glass is affected. Therefore, the content of ZnO in the component is 8% -30%, preferably 10% -28%, and more preferably 12% -25%.
In the invention, znO and SiO 2 Ratio ZnO/SiO 2 When the glass is too low, the cut-off performance of the glass cannot meet the design requirement, znO/SiO 2 When the value of (B) is too high, the crystallization property and the crystallization stability of the glass become poor, so that ZnO/SiO 2 0.1 to 1, preferably 0.2 to 0.8, and more preferably 0.3 to 0.7.
The inventors found that MgO, caO, baO and SrO can reduce the high-temperature viscosity of the glass and promote the melting of the quantum dot components in the glass, but the excessive content can lead to the poor crystallization performance and the poor chemical stability of the glass. Therefore, in the present invention, the sum of the contents of MgO, caO, baO and SrO is from 0 to 8%, preferably from 0 to 6%, more preferably from 0 to 4%, of MgO+CaO+BaO+SrO.
MgO improves the chemical stability of the glass, but the crystallization property of the glass with higher content is poor, and the cut-off property of the glass does not meet the design requirement, so that the MgO content is 0 to 2%, preferably 0 to 1.5%, and more preferably 0 to 1%.
CaO, baO and SrO can improve crystallization performance of glass, reduce high-temperature viscosity of the glass, but the content is too high, so that the chemical stability of the glass is poor, the formation of a coloring matter structure is disturbed, and the cut-off performance of the glass is reduced. Therefore, the content of CaO, baO and SrO is 0 to 2%, preferably 0 to 1.5%, and more preferably 0 to 1%.
CdS is one of the quantum dot components, and can cause the glass to absorb at 470nm to 500nm in a cut-off way. In the invention, cdS mainly plays a role of a reducing agent, and can avoid quantum dot component Se in glass 2- 、Te 2- Oxidized and can also provide the formation of quantum dots Cd 2+ . However, the crystallization performance of the glass is poor due to the excessively high CdS content, and meanwhile, S has strong absorption in a near infrared region, so that the transmittance of the glass in the near infrared region can be reduced, and the transmittance performance of the glass cannot meet the design requirement. Therefore, the content of CdS in the component is 1-10%, preferably 2-8%, and more preferably 2-6%.
Se is one of the quantum dot components in the glass of the invention, and is combined with Cd in the glass 2+ The formation of CdSe quantum dot crystals can cause the glass to absorb at 500 nm-680 nm. If the Se content is too high, the crystallization property of the glass is poor and the near infrared transmittance does not meet the design requirements, so that the Se content is preferably 0.4 to 5%, more preferably 0.7 to 4%, still more preferably 0.8 to 3.5%. The Se content refers to the content of all selenium-containing substances in the glass, which is converted into elemental selenium. Se is introduced in the form of elemental selenium and/or selenium-containing compounds in the present invention.
Te is one of the quantum dot components in the glass of the invention, and Cd in the glass 2+ The CdTe quantum dot crystal can cause the 500 nm-830 nm cut-off absorption of glass. If Te is too high, it enters the glass network structure to lower the stability of the glass and the near infrared transmittance does not meet the design requirements, so that the Te content is preferably 0.5 to 5%, more preferably 0.7 to 4%, still more preferably 0.8 to 3%. The Te content in the invention refers to the content of all selenium-containing substances in the glass, which are completely converted into simple substance tellurium. Te in the invention is introduced in the form of simple substance tellurium and/or tellurium-containing compounds.
According to the invention, through a large number of experimental researches, when the content ratio Se/Te of Se and Te is too high, the cut-off wavelength position of the glass is smaller than 650nm, and the transmittance cannot meet the design requirement. Therefore, se/Te is preferably less than 2.0, more preferably less than 1.5, and even more preferably less than 1.
Further, when the ratio Σ (se+te)/CdS of the sum of the Se and Te to CdS is too low, the cut-off wavelength position of the glass is less than 650nm, the transmittance cannot meet the design requirement, the ratio Σ (se+te)/CdS of the sum of the Se and Te to CdS is more than 0.05, preferably more than 0.1, more preferably Σ (se+te)/CdS is more than 0.2.
Further, in the present invention, when the thickness of the filter glass is 2mm, the cut-off wavelength is 600nm or more, preferably 650nm or more, more preferably 700nm or more, and still more preferably 750nm or more.
When the thickness of the filter glass is 2mm, the transmittance at 850 to 900nm is 80% or more, preferably 82% or more, more preferably 84% or more; the transmittance at 900 to 950nm is 85% or more, preferably 86% or more, more preferably 87% or more; the transmittance at 950 to 2000nm is 88% or more, preferably 89% or more, and more preferably 90% or more.
In the present invention, the acid resistance of the filter glass is 3 or more, preferably 2 or more, and more preferably 1; the water resistance of the filter glass is 3 or more, preferably 2 or more, and more preferably 1;
the Young's modulus of the filter glass is 61GPa or more, preferably 63GPa or more, and more preferably 64GPa or more;
expansion coefficient alpha of the filter glass 20-300℃ 80X 10 -7 above/K, preferably 85X 10 -7 Preferably above/K, more preferably 90X 10 -7 and/K.
Further, the invention also provides a preparation method of the filter glass, which comprises the following steps:
uniformly mixing the raw materials of the components of the filter glass according to a proportion, and putting the mixture into a melting furnace at 1200-1400 ℃ for melting to form molten glass;
homogenizing the molten glass to eliminate bubbles in the glass;
casting or leaking homogenized molten glass into a mold for molding to obtain a molded body;
and (3) placing the formed body into an annealing furnace, preserving heat for 24-72h at 550-700 ℃ to carry out nucleation reaction on the glass, and preserving heat for 12-72h at 550-700 ℃ to enable crystals in the glass to grow up to obtain the filter glass with special permeation.
In the present invention, the raw materials of the filter glass may use a composite salt (e.g., carbonate, phosphate, nitrate, etc.), and/or hydroxide, and/or oxide, and/or sulfide, and/or selenide, and/or fluoride, and/or simple substance, etc.
The invention also provides an optical element comprising the filter glass according to the invention. In the present invention, the optical element may include a glass element and a glass preform.
Specifically, the glass preform can be produced by using a means such as polishing, or by using a means such as reheat press molding, precision press molding, or the like. That is, the glass preform may be produced by mechanically working glass such as grinding and polishing, or by producing a preform for press molding from glass, and then performing polishing after hot press molding, or by performing precision press molding on a preform produced by performing polishing. The means for producing the glass preform is not limited to the above-described means.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Examples 1 to 21
The filter glasses of examples 1 to 21 were prepared according to the proportions shown in tables 1 to 3 as follows.
1) Uniformly mixing the raw materials of each component of the filter glass in proportion, and putting the mixture into a melting furnace at 1300 ℃ for melting to form molten glass;
2) Stirring and homogenizing the molten glass to eliminate bubbles in the glass;
3) Pouring or leaking the homogenized molten glass into a mould for molding to obtain a molded body;
4) And (3) placing the formed body into an annealing furnace, preserving heat for 30 hours at 600 ℃ to carry out nucleation reaction on the glass, and preserving heat for 20 hours at 650 ℃ to enable crystals in the glass to grow up to obtain the special-permeation optical filter glass.
Performance detection
1. Cut-off performance
The 2mm glass sample was tested for transmittance curves of 240nm to 2000nm for glass using a spectrometer according to the GB/T7962.12-2010 method, with the transmittance at 5% becoming the cut-off wavelength. For the present invention, the higher the cutoff value, the better the cutoff performance of the glass, the lower the cutoff value, the worse the cutoff performance, and the detection results are shown in table 1.
2. Transmittance of glass
The 2mm glass sample is used for testing the transmittance curve of 240 nm-2000 nm of glass by using a spectrometer according to the GB/T7962.12-2010 method, and the near infrared transmittance of the invention refers to transmittance values of 850 nm-2000 nm. The near infrared transmittance of the invention refers to the lowest transmittance in the corresponding band range, and the detection results are shown in table 1.
3. Stability of acid resistance
Acid resistance stability of glass (D A ) (powder method) the test was carried out according to the method specified in GB/T17129, and the test results are shown in Table 1.
4. Stability of Water resistance
The stability of the water resistance (DW) of the glass (powder method) was tested according to the method specified in GB/T17129. The stability of the water resistance in the present invention is sometimes simply referred to as water resistance or water resistance stability, and the test results are shown in Table 1.
5. Young's modulus
Young's modulus E of the glass was measured according to the method specified in GB/T7962.6, and the measurement results are shown in Table 1.
6. Coefficient of thermal expansion
The thermal expansion coefficient refers to the average thermal expansion coefficient of 20-300 ℃ of glass, and alpha is adopted 20-300℃ The test results are shown in Table 1, which shows that the test was conducted according to the method specified in GB/T7962.16-2010.
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from examples 1 to 21, the filter glass of the present invention has a cut-off wavelength of 600nm or more, a transmittance of 850 to 900nm of 80% or more, a transmittance of 900 to 950nm of 85% or more, and a transmittance of 950 to 2000nm of 88% or more when the filter glass has a thickness of 2 mm. Meanwhile, the glass material also shows good chemical stability and mechanical properties.
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. The filter glass is characterized by comprising the following components in percentage by weight:
SiO 2 :30% -70%, preferably 35% -68%, more preferably 38% -65%;
B 2 O 3 :3% -20%, preferably 4% -15%, more preferably 5% -10%;
ZnO:8 to 30%, preferably 10 to 28%, more preferably 12 to 25%;
CdS:1 to 10%, preferably 2 to 8%, more preferably 2 to 6%;
se:0.4 to 5%, preferably 0.7 to 4%, more preferably 0.8 to 3.5%;
te:0.5 to 5%, preferably 0.7 to 4%, more preferably 0.8 to 3%;
Al 2 O 3 :0 to 3%, preferably 0 to 2%, more preferably 0 to 1%;
Li 2 O、Na 2 O、K 2 sum of O contents Li 2 O+Na 2 O+K 2 O is 5% -28%, preferably 7% -23%, more preferably 9% -20%;
the sum of MgO, caO, baO and SrO content is MgO+CaO+BaO+SrO 0 to 8%, preferably 0 to 6%, more preferably 0 to 4%.
2. The filter glass according to claim 1, wherein, in weight percent, li 2 The O content is 0 to 3%, preferably 0 to 1%, more preferably not incorporated; na (Na) 2 The content of O is 2 to 9%, preferably 3 to 8%, more preferably 4 to 8%; k (K) 2 The content of O is 3 to 16%, preferably 4 to 14%, more preferably 5 to 12%; and/or the number of the groups of groups,
the content of MgO in the filter glass is 0-2%, preferably 0-1.5%, more preferably 0-1% by weight; the CaO content is 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%; the SrO content is 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%; the BaO content is 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%.
3. The filter glass according to claim 1 or 2, wherein the weight percentage of SiO 2 And Al 2 O 3 Sum of the contents of (B) and B 2 O 3 、Li 2 O、Na 2 O and K 2 Ratio of sum of O contents Sigma (SiO) 2 +Al 2 O 3 )/∑(B 2 O 3 +Li 2 O+Na 2 O+K 2 O) is 0.5 to 3.0, preferably 0.8 to 2.5, more preferably 1 to 2.2.
4. A filter glass according to any one of claims 1 to 3, wherein the percentages by weight of ZnO and SiO are 2 Ratio ZnO/SiO 2 From 0.1 to 1, preferably from 0.2 to 0.8, more preferably from 0.3 to 0.7.
5. The filter glass according to any of claims 1 to 4, wherein the ratio Se/Te of Se to Te content is less than 2.0, preferably less than 1.5, more preferably less than 1, in weight percent.
6. Filter glass according to any of claims 1 to 5, characterized in that the ratio Σ (se+te)/CdS of the sum of Se and Te contents to CdS is greater than 0.05, preferably greater than 0.1, more preferably Σ (se+te)/CdS is greater than 0.2 in weight percent.
7. The filter glass according to any one of claims 1 to 6, wherein when the thickness of the filter glass is 2mm, the cut-off wavelength thereof is 600nm or more;
when the thickness of the filter glass is 2mm, the transmittance of 850-900 nm is more than 80%, the transmittance of 900-950 nm is more than 85%, and the transmittance of 950-2000 nm is more than 88%.
8. The filter glass according to any one of claims 1 to 7, wherein the filter glass has an acid resistance of 3 or more types; the water resistance of the filter glass is more than 3 types;
the Young's modulus of the filter glass is more than 61 GPa;
expansion coefficient alpha of the filter glass 20-300℃ 80X 10 -7 and/K.
9. A method for producing the filter glass according to any one of claims 1 to 8, comprising the steps of:
uniformly mixing the raw materials of all the components of the glass according to a proportion, and putting the mixture into a melting furnace at 1200-1400 ℃ for melting to form molten glass;
homogenizing the molten glass to eliminate bubbles in the glass;
casting or leaking homogenized molten glass into a mold for molding to obtain a molded body;
and (3) placing the formed body into an annealing furnace, preserving heat for 24-72h at 550-700 ℃ to carry out nucleation reaction on the glass, and preserving heat for 12-72h at 550-700 ℃ to enable crystals in the glass to grow up to obtain the filter glass.
10. An optical element comprising the filter glass according to any one of claims 1 to 8.
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| CN202310407900.7A CN116573849A (en) | 2023-04-12 | 2023-04-12 | Optical filter glass, preparation method thereof and optical element |
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