CN117550803A - Ultraviolet-transmitting glass and preparation method and application thereof - Google Patents
Ultraviolet-transmitting glass and preparation method and application thereof Download PDFInfo
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- CN117550803A CN117550803A CN202310902439.2A CN202310902439A CN117550803A CN 117550803 A CN117550803 A CN 117550803A CN 202310902439 A CN202310902439 A CN 202310902439A CN 117550803 A CN117550803 A CN 117550803A
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- 239000011521 glass Substances 0.000 title claims abstract description 249
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 33
- 230000008018 melting Effects 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000002516 radical scavenger Substances 0.000 claims abstract description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 10
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000002834 transmittance Methods 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 36
- 239000000156 glass melt Substances 0.000 claims description 18
- 230000003287 optical effect Effects 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001459 lithography Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 58
- 239000000126 substance Substances 0.000 abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 88
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 229910000833 kovar Inorganic materials 0.000 description 5
- 238000010309 melting process Methods 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000006854 communication Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000005365 phosphate glass Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002211 ultraviolet spectrum 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0085—Compositions for glass with special properties for UV-transmitting 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses ultraviolet-transmitting glass and a preparation method and application thereof. The preparation method of the ultraviolet transmission glass comprises the following steps: mixing the raw materials comprising the following components: 30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 Totaling 100wt%; and adding an impurity scavenger, and melting under negative pressure, wherein the impurity scavenger comprises graphite and chloride. The invention adds impurities by reasonably designing componentsThe scavenger is melted at high temperature under vacuum, which can obviously reduce the impurity content in the glass, thereby realizing the ultraviolet transmission glass with improved ultraviolet transmission performance, good chemical stability and matched thermal expansion coefficient with simple process steps.
Description
Technical Field
The invention relates to the technical field of ultraviolet-transmitting glass, in particular to ultraviolet-transmitting glass and a preparation method and application thereof.
Background
Ultraviolet is an electromagnetic wave commonly existing in the nature, and can be widely applied to the fields of ultraviolet curing, missile early warning, biomedical treatment, biological detection, non-line-of-sight secret communication, photocatalysis, sterilization, purification and the like. Due to the action of atmospheric molecules and particles, ultraviolet rays with the wavelength of about 200-280nm in the sunlight spectrum can be strongly absorbed by ozone layers in the atmosphere, so that the effect of protecting human beings is achieved, and the ultraviolet spectrum region is also called a solar blind region. Ultraviolet radiation in this band is almost absent from the near-earth atmosphere and is presumed to be produced by human activity such as the firing of artificial aircraft such as missiles, rockets, and the like if a "solar dead zone" ultraviolet signal is detected in the atmosphere. Therefore, the method has great significance for detecting the ultraviolet rays of the 'daily blind areas'.
Most colorless optical glasses have high transmittance in the visible range, but have different degrees of absorption of ultraviolet light. The energy of ultraviolet rays in the wave band of 200-280nm is 4.4-6.2eV, and the forbidden bandwidth of the common optical glass is smaller than 4.4eV, electrons can be excited to transition between energy levels under the irradiation of the ultraviolet rays with high energy so as to absorb the ultraviolet rays, so that the ultraviolet rays in the wave band are difficult to penetrate through the common glass, and only a few glasses containing special components have better ultraviolet transmittance performance. Single SiO 2 、B 2 O 3 And P 2 O 5 The ultraviolet transmission cutoff wavelength of the glass is 160nm, 170nm and 145nm respectively, has higher ultraviolet transmission,it is therefore expected that high-performance ultraviolet-transmitting glass can be produced by properly designing glass components.
The factors influencing the ultraviolet transmittance of ultraviolet-transmitting glass are many, and besides the glass components, harmful impurities such as Fe and the like contained in the glass are also an important factor. Even if only a small amount of impurities are present, the ultraviolet transmission properties of the glass are severely affected. Therefore, harmful impurities are minimized or removed throughout the glass production process to reduce its impact on the glass properties.
Disclosure of Invention
In view of the above, the present invention is mainly aimed at providing an ultraviolet-transmitting glass, a preparation method and an application thereof, and the technical problem to be solved is how to realize the production of an ultraviolet-transmitting glass with excellent ultraviolet-transmitting performance and suitable thermal expansion coefficient under the conditions of simplifying the process steps and reducing the cost, so as to meet the requirements of development of the fields of ultraviolet detection and the like on ultraviolet-transmitting glass materials.
The aim of the invention and the solution of the technical problems are achieved by adopting the following technical proposal. The preparation method of the ultraviolet transmission glass provided by the invention comprises the following steps:
mixing raw materials comprising the following components: 30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 Totaling 100wt%; and
adding impurity scavenger, melting under negative pressure to obtain the ultraviolet transmitting glass,
wherein the impurity scavenger comprises graphite and chloride.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the aforementioned method for producing an ultraviolet-transmitting glass, wherein the method comprises the steps of:
1) Weighing the components in the raw materials according to the proportion, and mixing;
2) Adding the impurity scavenger to obtain a mixture;
3) Placing the mixture into a melting furnace, vacuumizing, and melting the mixture under negative pressure to obtain a glass melt;
4) And clarifying the glass melt, forming by material leakage, and annealing to obtain the ultraviolet-transmitting glass.
Preferably, in the aforementioned method for preparing an ultraviolet-transmitting glass, in the step 2), the chloride is at least one selected from sodium chloride, potassium chloride, ammonium chloride, calcium chloride, and magnesium chloride.
Preferably, in the aforementioned method for preparing an ultraviolet-transmitting glass, in the step 2), the graphite is used in an amount of 0.5 to 1.0wt% and the chloride is used in an amount of 0.3 to 0.8wt% based on the total weight of the raw materials.
Preferably, in the aforementioned method for producing ultraviolet-transmitting glass, in the step 3), the vacuum degree of the melting furnace is from-0.05 MPa to-0.01 MPa.
Preferably, in the aforementioned method for preparing ultraviolet-transmitting glass, in the step 3), the melting temperature is 1450-1550 ℃ and the time is 2-4h.
Preferably, in the aforementioned method for preparing ultraviolet-transmitting glass, in the step 4), the annealing temperature is 490-530 ℃ and the time is 3-5h.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the invention, the ultraviolet-transmitting glass comprises the following components in percentage by weight: 30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 A total of 100wt%,
wherein, the raw material is added with an impurity scavenger containing graphite and chloride,
wherein, in the ultraviolet-transmitting glass, fe element as impurity is Fe 2 O 3 The content by weight is less than 1.0ppm based on the total weight of the ultraviolet-transmitting glass.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the aforementioned ultraviolet-transmitting glass, wherein the ultraviolet-transmitting glass is produced by any one of the methods described above.
Preferably, the ultraviolet-transmitting glass as described above, wherein the ultraviolet-transmitting glass has a coefficient of thermal expansion of (50.+ -. 1). Times.10 -7 The transmittance of ultraviolet rays in the wavelength range of 200-275nm at the thickness of 2.0mm is more than 82 percent at the temperature of/DEG C.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the invention, an optical device comprises a high ultraviolet transmission window, a lamp tube or a camera lens, wherein the high ultraviolet transmission window, the lamp tube or the camera lens comprises any one of the ultraviolet transmission glass.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the aforementioned optical device, wherein the optical device is an ultraviolet detector, a large scale integrated circuit lithography, an ultraviolet optical lens or an ultraviolet spectrometer.
The invention reduces or removes harmful impurities (such as iron and the like) in glass by reasonably designing glass components and introducing an impurity scavenger, thereby preparing the high-performance ultraviolet-transmitting glass. P (P) 2 O 5 The ultraviolet transmission cutoff wavelength of the glass is 145nm, the ultraviolet transmittance is higher, the thermal expansion coefficient is larger, but the chemical stability is poor, and the pure phosphate glass has no great practical value. Therefore, siO with good chemical stability and high ultraviolet transmittance is introduced 2 Silicophosphate glass was prepared. At the same time, in order to ensure the stable structure of the glass, al is introduced 2 O 3 And Li (lithium) 2 O regulates the glass structure and proper amount of Li 2 O replaces P in silicophosphate glass systems 2 O 5 Changeable glassThe network structure of the glass has the advantages of good chemical stability, high deep ultraviolet transmittance (200-275 nm wave band), matching of thermal expansion coefficient and kovar alloy, and the like. In addition to being related to the glass composition, the actual ultraviolet transmittance of the glass is also affected by trace impurities, mainly variable valence ions of different valence states, including transition metal Fe, etc. These impurities may be introduced by the raw materials or from contamination of the melting technology and processing methods. The effect of trace impurities is deeply eliminated by introducing an impurity scavenger comprising graphite and chloride, wherein the graphite can act as a reducing agent to reduce Fe in the glass melt 3+ The Fe is made into Fe simple substance to be precipitated to the bottom of the crucible; meanwhile, graphite can also form P-O-C bond in phosphate, and carbon atoms are combined into a glass network to capture electrons in non-bridging oxygen, so that the ultraviolet transmission performance of the glass is improved. The chloride reacts chemically with the iron element in the glass melt at high temperatures to form volatile reaction products. The influence of trace impurities on the ultraviolet ray transmission performance of the glass can be obviously reduced or even eliminated through the combined action of the graphite and the chloride, and the ultraviolet ray transmission rate of the glass is improved. In fact, in the impurity scavenger according to the present invention, graphite and chloride show a certain synergistic effect for eliminating the influence of impurities and improving the glass properties. For example, in the case of using graphite and chloride at the same time to eliminate impurities, the ultraviolet-transmitting property of the glass is significantly superior to that of the glass when graphite or chloride is used alone.
By means of the technical scheme, the ultraviolet-transmitting glass and the preparation method and application thereof have at least the following beneficial effects:
according to the ultraviolet-transmitting glass and the preparation method thereof, the glass components and the content are reasonably designed, so that the prepared glass has excellent ultraviolet-transmitting performance, and the thermal expansion coefficient is matched with that of the kovar alloy, so that the performance requirements of the application fields such as ultraviolet detection can be met.
According to the ultraviolet-transmitting glass and the preparation method thereof, the impurity scavenger is introduced and the glass is melted at high temperature under vacuum, so that harmful impurities can be efficiently and deeply separated from glass melt, and iron removal treatment on glass raw materials is not needed in advance, thereby reducing the steps of glass preparation process, lowering the cost and effectively improving the ultraviolet-transmitting performance of the glass.
The foregoing description is only an overview of the present invention, and is intended to provide a more clear understanding of the technical means of the present invention, and is to be implemented in accordance with the teachings of the present invention, as set forth in detail in the following description of the preferred embodiments of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the present invention, the following describes the specific implementation, structure, characteristics and effects of the polarizing glass and the preparation method and application thereof according to the present invention in detail with reference to the preferred embodiments. In the following description, reference to "an embodiment" or "an embodiment" does not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
In the examples of the present invention, unless otherwise specified, materials, reagents, etc. are commercially available products well known to those skilled in the art; unless otherwise indicated, all methods referred to are known in the art. Unless defined otherwise, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The invention provides a preparation method of ultraviolet-transmitting glass, which comprises the following steps:
mixing raw materials comprising the following components: 30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 Totaling 100wt%; and
adding impurity scavenger, melting under negative pressure to obtain the ultraviolet transmitting glass,
wherein the impurity scavenger comprises graphite and chloride.
The functions of the components in the raw materials are as follows:
P 2 O 5 the oxide is a network generating body oxide, has the ultraviolet transmission cutoff wavelength of only 145nm, can be used as a main body of a framework structure formed by glass, and is a main component for improving the ultraviolet transmission rate. P (P) 2 O 5 In the network structure of glass, the [ PO ] is generally double-bonded 4 ]Tetrahedrons are connected by the cell's top corners. If P 2 O 5 If the content is less than 30wt%, it is difficult to obtain ultraviolet glass having high transmittance; if P 2 O 5 When the content is more than 50% by weight, the refractive index of the glass decreases, the thermal expansion coefficient increases, and the chemical stability of the glass decreases, and the crystallization resistance deteriorates.
SiO 2 The ultraviolet transmission cutoff wavelength of the glass is 160nm, the glass has excellent ultraviolet transmission performance, is a main component forming a glass skeleton, and can form a uniform network inside the glass. The silicon oxygen tetrahedron is connected with the vertex angle of the phosphorus oxygen tetrahedron, so that the ultraviolet rays move to short waves through the cut-off wavelength. Incorporation of SiO into glass 2 Can improve the strength, viscosity and thermal stability of the glass and reduce the thermal expansion coefficient of the glass. If SiO is 2 If the content is less than 10wt%, the overall properties of the glass are deteriorated, and a glass having a high transmittance is not easily obtained; if SiO is 2 If the content is more than 20wt%, the temperature required in the glass melting process is too high, and stones and other defects are caused, so that the final properties of the glass are affected.
Al 2 O 3 Can be combined with SiO 2 And the network structure is formed together, so that the glass structure tends to be compact, and a series of properties of the glass are improved. At the same time Al 2 O 3 Free oxygen in the glass can be abstracted to form an aluminum oxide tetrahedron, and the aluminum oxide tetrahedron is similar to a silicon oxide tetrahedron structure, can play a role in improving and strengthening the structure of phosphate glass, and can improve the ultraviolet transmittance and chemical stability of the glass. If Al is 2 O 3 The content is lower than 5wt percent, so that the internal network structure degree of the glass is low, the performances of strength, viscosity, ultraviolet transmittance and the like are poor, and meanwhile, the network gap is small. If Al is 2 O 3 If the content is more than 10% by weight, the temperature required for melting the glass becomes too high and the glass becomesCausing the defects of stones and the like, reducing the thermal expansion coefficient of the glass and having poor matching property with the kovar alloy, thereby influencing the final performance of the glass.
B 2 O 3 The ultraviolet transmittance of the glass can be effectively improved when the ultraviolet transmittance cutoff wavelength is 170nm, and the glass is one of important components of the glass and is also a good fluxing agent. B (B) 2 O 3 Forming boron-oxygen tetrahedra in the glass, so that the structure tends to be compact and the viscosity of the glass is improved; introduction of B 2 O 3 Can repair the broken net structure inside the glass, strengthen the three-dimensional skeleton structure of the glass and is beneficial to ultraviolet wave transmission. If B 2 O 3 If the content is more than 20wt%, the temperature required in the glass melting process is too high, and the glass structure is weakened by the boron-oxygen tetrahedron rather than the boron-oxygen tetrahedron, so that the performance is reduced and phase separation occurs. If B 2 O 3 If the content is less than 10wt%, sufficient boron-oxygen tetrahedra cannot be formed in the glass, so that the boron structure is changed from a layered structure to a frame-like structure, and the broken network structure of the glass cannot be repaired, resulting in a decrease in ultraviolet transmitting performance.
MgO is an external oxide of a glass structure network, and can raise the softening temperature of glass and reduce the thermal expansion coefficient, and contains P 2 O 5 MgO is introduced into the glass of the steel sheet to make the structure tend to be strong. If the MgO content is less than 1 weight percent, the lifting effect is not obvious; if the MgO content is higher than 5wt%, the magnesia tetrahedra enter the glass network, which in turn reduces the chemical stability and hardness of the glass.
CaO is an oxide of an external network of a glass structure, and can increase the chemical stability and the mechanical strength of the glass. If the CaO content is lower than 5 weight percent, the lifting effect is not obvious; if the CaO content is more than 10% by weight, the chemical resistance of the glass is lowered, and the crystallization tendency of the glass is increased.
Li 2 Li in O + The ion radius is small, the electric field intensity is large, the chemical stability and the surface tension of the glass can be improved, the glass has the function of high-temperature fluxing, and the high-temperature viscosity of the glass is reduced. Proper amount of Li 2 O replaces P in silicophosphate glass systems 2 O 5 Changeable glassThe network structure of the polymer has the advantages of good chemical stability and high deep ultraviolet transmittance. When the glass system also contains B 2 O 3 And SiO 2 When Li is added 2 O repairable [ PO ] 4 ]、[SiO 4 ]And [ BO ] 3 ]The break points between the two parts strengthen network connection and reduce the quantity of non-bridging oxygen; and with Li 2 The increased O introduction plays a role in network bond breaking and generates non-bridging oxygen. The non-bridging oxygen has close relation with the ultraviolet-transmitting performance of the glass, the transmittance is reduced when the non-bridging oxygen is more, and the transmittance is increased when the non-bridging oxygen is less. If Li 2 The O content is less than 3wt%, so that the expected effect cannot be achieved; if Li 2 If the O content is more than 8wt%, the crucible is severely corroded, and the ultraviolet ray transmitting performance of the glass is lowered.
La 2 O 3 Is lanthanide rare earth oxide, belonging to high refractive index low dispersion oxide. La (La) 3+ The ion radius is large, and the electric field intensity ensures that stronger aggregation is generated in the glass, so that the refractive index and the ultraviolet transmittance of the glass can be increased. If La is 2 O 3 The content is lower than 2 weight percent, so that the effect of improving the ultraviolet transmittance is not obvious; if La is 2 O 3 If the content is more than 8wt%, the glass tends to be devitrified.
Y 2 O 3 The rare earth oxide can increase the refractive index of the glass, reduce the melting temperature and crystallization temperature of the glass and increase the thermal expansion coefficient. If Y 2 O 3 The content is lower than 2 weight percent, so that the effect of improving the ultraviolet transmittance is not obvious; if Y 2 O 3 If the content is higher than 8wt%, the glass is liable to devitrify, and the expansion coefficient is too large, which affects the matching with the kovar alloy.
In some embodiments, the method comprises the steps of:
1) Weighing the components in the raw materials according to the proportion, and mixing;
2) Adding the impurity scavenger to obtain a mixture;
3) Placing the mixture into a melting furnace, vacuumizing, and melting the mixture under negative pressure to obtain a glass melt;
4) And clarifying the glass melt, forming by material leakage, and annealing to obtain the ultraviolet-transmitting glass.
In step 2) of some embodiments, the chloride may be selected from at least one of sodium chloride, potassium chloride, ammonium chloride, calcium chloride, magnesium chloride; the graphite is used in an amount of 0.5 to 1.0wt% and the chloride is used in an amount of 0.3 to 0.8wt% based on the total weight of the raw materials. The graphite can be used as a reducing agent for reducing Fe element impurities in glass melt, and the Fe element impurities are reduced into iron simple substances to be precipitated at the bottom of a crucible, so that trace impurities in glass caused by raw materials or introduced in the melting process are eliminated; at the same time, graphite can also form P-O-C bonds in phosphate, and carbon atoms are combined into a glass network to capture electrons in non-bridging oxygen, so that the ultraviolet transmission performance of the glass is improved. If the content of graphite is less than 0.5wt%, the impurity removal effect is not obvious, and the ultraviolet-transmitting performance of the glass cannot be effectively improved; if the content of graphite is more than 1.0wt%, graphite reacts with the glass component to generate excessive bubbles to affect the glass properties, and cannot be completely melted in the glass melt, thereby forming stones or defects. The chloride can react with iron element in the glass melt at high temperature to form volatile products, so that impurity iron in the glass is eliminated, and the ultraviolet transmittance of the glass is improved. If the chloride content is less than 0.3wt%, the effect of removing impurities is not obvious; if the chloride content is higher than 0.8wt%, the crucible is eroded and the ultraviolet transmitting property of the glass is lowered.
In step 3) of some embodiments, the melting furnace has a vacuum of from-0.05 MPa to-0.01 MPa. The purpose of keeping the melting furnace at a certain vacuum degree in the glass melting process is to make volatile substances generated by reaction volatilize from the glass melt more easily, thereby being beneficial to promoting the reduction or removal of impurity iron in the glass melt and improving the degree and efficiency of iron separation. If the vacuum degree is more than-0.01 MPa, the volatilization promoting effect of the impurity iron on the volatile product is not obvious; if the vacuum degree is less than-0.05 MPa, other substances in the glass melt are volatilized, so that the control of glass components is not facilitated, meanwhile, the requirement on equipment is high, the cost is increased, and the efficiency is reduced.
In step 3) of some embodiments, the melting temperature is 1450-1550 ℃ for 2-4 hours. The glass component contains refractory components such as silicon oxide, aluminum oxide and the like. If the melting temperature is lower than 1450 ℃, the glass viscosity is high, uniform glass melt is difficult to form, and the generated volatile substances are difficult to completely remove; if the melting temperature is higher than 1550 ℃, the volatility of the glass components is increased, thereby affecting the final composition of the glass and increasing the energy consumption. If the melting time is less than 2 hours, the homogenization of the glass is not completed, and the uniformity of the glass is affected; if the melting time is greater than 4 hours, the reaction is completed and the efficiency is reduced by continuing to increase the time.
In step 4) of some embodiments, the annealing is at a temperature of 490 to 530 ℃ for a time of 3 to 5 hours. Annealing is performed to eliminate internal stresses present in the glass. If the annealing temperature is lower than 490 ℃, inefficiency is caused; if the annealing temperature is higher than 530 ℃, the energy consumption is too high, and new internal stress is generated in the glass. If the annealing time is less than 3 hours, the effect of eliminating the internal stress cannot be achieved; if the annealing time is longer than 5 hours, the effect of eliminating the internal stress is not increased any more.
The invention also provides ultraviolet-transmitting glass, which comprises the following components in percentage by weight: 30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 A total of 100wt%,
wherein, the raw material is added with an impurity scavenger containing graphite and chloride,
wherein, in the ultraviolet-transmitting glass, fe element as impurity is Fe 2 O 3 The content by weight is less than 1.0ppm based on the total weight of the ultraviolet-transmitting glass.
In some embodiments, the ultraviolet-transmitting glass is prepared by any of the methods described above.
As previously described, the method of producing ultraviolet-transmitting glass of the present invention uses an impurity scavenger to remove harmful impurities such as elemental iron and the like in the glass, wherein the impurity scavenger comprises graphite and chloride, which act together in different ways to deeply remove elemental iron from the glass melt, thereby significantly reducing or even eliminating the effect of trace impurities on the ultraviolet-transmitting properties of the glass.
In some embodiments, in the ultraviolet-transmitting glass, the impurity Fe element is Fe 2 O 3 The content by weight is less than 1.0ppm based on the total weight of the ultraviolet-transmitting glass.
In some preferred embodiments, in the ultraviolet-transmitting glass, the impurity Fe element is Fe 2 O 3 The calculated amount is less than 0.7ppm, for example less than 0.5ppm or 0.1ppm based on the total weight of the ultraviolet-transmitting glass.
In some embodiments, the ultraviolet-transmitting glass has a coefficient of thermal expansion of (50.+ -. 1). Times.10 -7 The transmittance of ultraviolet rays in the wavelength range of 200-275nm at the thickness of 2.0mm is more than 82 percent at the temperature of/DEG C.
The invention also provides an optical device which comprises a high ultraviolet transmission window, a lamp tube or a camera lens, wherein the high ultraviolet transmission window, the lamp tube or the camera lens comprises any ultraviolet transmission glass.
In some embodiments, the optical device is an ultraviolet detector, a large scale integrated circuit lithography, an ultraviolet optical lens, an ultraviolet spectrometer, or the like. The ultraviolet detector can be used in the ultraviolet early warning fields such as solar blind ultraviolet missile warning systems, power grid safety monitoring, forest fire warning and the like; the large-scale integrated circuit lithography can be used in the fields of electronic communication and the like; the ultraviolet optical lens and the ultraviolet spectrometer can be used in the fields of ultraviolet optical performance test or detection and the like.
The invention will be further described in connection with specific examples which are not to be construed as limiting the scope of the invention. Some insubstantial modifications and adaptations of the invention as described above would be within the scope of the invention.
Transmittance test: and testing the luminous flux or the light energy of the incident light after passing through the object, and comparing the test value with the total luminous flux or the light energy of the incident light, thereby obtaining the transmittance of the object. Firstly, directly testing the luminous flux or the light energy of incident light without passing through a sample to obtain reference illumination data; and then testing the luminous flux or the light energy of the incident light after passing through the object to obtain test illumination data. Specifically, incident light was irradiated onto the ultraviolet-transmitting glass prepared in each example covering the light inlet, light transmitted through the glass prepared in each example was collected, and then entered into the detector through the detection port, and outgoing light data was detected using the detector, wherein the wavelength of the incident light for the test was in the range of 160-1100 nm.
Coefficient of thermal expansion test: and (3) placing the sample to be tested into a heating furnace for heating, and transmitting the expansion amount to a displacement sensor through a push rod after the sample is heated and expanded along with the temperature rise, wherein the displacement amount measured by the displacement sensor is the displacement amount of the thermal expansion change of the sample. Along with the rise of the temperature of the furnace body, the system respectively transmits the changed temperature signal and the displacement signal to a computer in real time through data acquisition and processing, and the thermal expansion coefficient of the sample is obtained through calculation of a thermal expansion formula.
Testing the Fe content in glass: measuring stable absorption in the 700-1100nm area by using a spectrophotometer, calculating the difference between absorbance at 1050nm and 770nm, and calculating the mass content of ferrous iron in the glass according to the linear relation between the ferrous iron mass content and the absorbance difference; measuring a transmittance curve in a wave band of 350-1050nm, recording the transmittance at 1000nm and 380nm, and calculating the mass content of ferric iron according to a ferrous iron-ferric iron ratio formula; the sum of the ferrous iron and ferric iron is the total iron content in the glass.
Example 1
Weighing the components in the raw materials according to the preset composition of the ultraviolet-transmitting glass, and uniformly mixing: 50wt% of P 2 O 5 10wt% SiO 2 10wt% of Al 2 O 3 16wt% of B 2 O 3 2wt% MgO,5wt% CaO,3wt% Li 2 O,2wt% Y 2 O 3 And2wt% of La 2 O 3 Wherein P is 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. Adding 0.5wt% of graphite and 0.3wt% of potassium chloride based on the total weight of the raw materials into the uniformly mixed raw materials, and then placing the raw materials into a melting furnace to be melted for 2 hours at a high temperature of 1500 ℃, wherein the vacuum degree of the melting furnace is kept to be-0.01 MPa in the melting process. And clarifying the glass melt obtained by melting, forming by material leakage, and then annealing at 490 ℃ for 3 hours to obtain the ultraviolet transmission glass. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.5 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at 2.0mm thickness of 82.8%, thermal expansion coefficient of 50.5X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 2
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 225g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.4ppm, a transmittance of 82.5% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.7X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 3
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that graphite was added in an amount shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.3 ppm), a transmittance of 83.0% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, and a thermal expansion coefficient of 50.3X10 -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 4
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the potassium chloride was added in an amount shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.5 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at 2.0mm thickness of 82.4%, thermal expansion coefficient of 50.8X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 5
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the temperature and time of melting were as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.6ppm, a transmittance of 82.2% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.8X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 6
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the vacuum degree during melting was as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.6ppm, a transmittance of 82.1% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.9X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 7
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the temperature and time of annealing are as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. Through testing, the prepared ultraviolet ray transmitsContent of Fe in the shot glass (in terms of Fe 2 O 3 Calculated as 0.5 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm of 82.6%, thermal expansion coefficient of 50.3X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 8
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 150g, and the rest components are corresponding. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.6 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm of 82.5%, thermal expansion coefficient of 50.5X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 9
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 225g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.7ppm, a transmittance of 82.7% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.1X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 10
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.6ppm, a transmittance of 82.9% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.1X10) -7 and/C. The prepared ultraviolet transmitting glass can be used for ultraviolet detectionThe high ultraviolet of the detector passes through the window.
Example 11
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 225g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.4ppm, a transmittance of 82.6% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.3X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 12
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 245g, and the rest components are corresponding. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.5 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at 2.0mm thickness of 82.2%, thermal expansion coefficient of 50.4X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 13
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the raw materials were each assigned as shown in Table 1, wherein P 2 O 5 The weight of the mixture is 240g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.3 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm of 82.3%, thermal expansion coefficient of 50.6X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 14
Ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the chloride species used was as shown in Table 2Shown, where P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.5 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at 2.0mm thickness of 82.8%, thermal expansion coefficient of 50.7X10 -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 15
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the chloride species used was as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.7ppm, a transmittance of 82.1% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.3X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 16
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the chloride species used was as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.4ppm, a transmittance of 82.3% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.6X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 17
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the chloride species used was as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.7ppm, against ultraviolet rays in the 200-275nm band at a thickness of 2.0 mm)Transmittance of 82.1% and thermal expansion coefficient of 50.5X10 -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Example 18
An ultraviolet-transmitting glass was produced by the same procedure as described in example 1, except that the temperature and time of melting were as shown in Table 2, wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The ultraviolet-transmitting glass prepared was tested for Fe content (in terms of Fe 2 O 3 Calculated as 0.8ppm, a transmittance of 82.5% for ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, a thermal expansion coefficient of 50.6X10) -7 and/C. The prepared ultraviolet transmission glass can be used for a high ultraviolet transmission window of an ultraviolet detector.
Comparative example 1
Preparation of glass samples was performed by the same procedure as described in example 1, except that no graphite was added to the starting material (as shown in Table 2), where P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The content of Fe (in Fe 2 O 3 Calculated as 40 ppm), transmittance of ultraviolet rays of 200-275nm band at a thickness of 2.0mm of 34.0%, thermal expansion coefficient of 50.9X10) -7 /℃。
Comparative example 2
Preparation of glass samples was performed by the same procedure as described in example 1, except that no chloride was added to the starting materials (as shown in Table 2), where P 2 O 5 Weighing 250g, and the rest components are corresponding. The content of Fe (in Fe 2 O 3 Measured at a concentration of 41 ppm), a transmittance of 39.8% for ultraviolet rays of 200 to 275nm wavelength band at a thickness of 2.0mm, and a thermal expansion coefficient of 51.1X10 -7 /℃。
Comparative example 3
Preparation of glass samples was performed by the same procedure as described in example 1, except that the melting furnace was not evacuated (as shown in Table 2), wherein P 2 O 5 The weight of the mixture is weighed to be 250g,the rest components are corresponding. The content of Fe (in Fe 2 O 3 Calculated as 35 ppm), transmittance of ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm of 41.1%, and thermal expansion coefficient of 51.2X10 -7 /℃。
Comparative example 4
The preparation of the glass sample was carried out by the same procedure as described in example 1, except that no chloride was added, and the amount of graphite added was equivalent to the total amount of chloride and graphite added in example 1 (as shown in Table 2), wherein P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The content of Fe (in Fe 2 O 3 Calculated as 28 ppm), transmittance of ultraviolet rays of 200 to 275nm wavelength band at a thickness of 2.0mm of 48.9%, and thermal expansion coefficient of 51.2X10 -7 /℃。
Comparative example 5
The preparation of the glass sample was carried out by the same procedure as described in example 1, except that graphite was not added, and the addition amount of the chloride was equivalent to the total addition amount of the chloride and graphite in example 1 (as shown in Table 2), in which P 2 O 5 The weight of the mixture is 250g, and the rest components correspond to each other. The content of Fe (in Fe 2 O 3 Calculated as 32 ppm), a transmittance of 43.8% to ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm, and a thermal expansion coefficient of 51.3X10 -7 /℃。
TABLE 1 raw material composition ratios of examples 1-18 and comparative examples 1-5
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TABLE 2 preparation process conditions for examples 1-18 and comparative examples 1-5
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As can be seen from the test data of examples 1 to 18, the ultraviolet-transmitting glass prepared by the method of the present invention has a transmittance of more than 82% for ultraviolet rays in the wavelength range of 200 to 275nm at a thickness of 2.0mm, and a thermal expansion coefficient of (50.+ -. 1). Times.10 -7 /℃。
As is apparent from the test data of comparative examples 1 to 3, comparative example 1, in which no graphite was added and only 0.3wt% of chloride was added, produced glass samples having a transmittance of 34.0% to ultraviolet rays in the 200-275nm band at a thickness of 2.0mm and a thermal expansion coefficient of 50.9X10, was compared with example 1 -7 and/C. Comparative example 2, in which no chloride was added and only 0.5% by weight of graphite was added, the glass sample prepared had a transmittance of 39.8% to ultraviolet rays of 200 to 275nm wavelength band at a thickness of 2.0mm, and a thermal expansion coefficient of 51.1X10 -7 and/C. Comparative example 3, in which the melting furnace was not evacuated, the glass sample prepared had a transmittance of 41.1% to ultraviolet rays of 200 to 275nm wavelength band at a thickness of 2.0mm, and a thermal expansion coefficient of 51.2X10 -7 /℃。
In addition, as can be seen from the test data of the above comparative examples 4 to 5, the same total amount of single graphite was used in comparative example 4 instead of the chloride and graphite in example 1, and the prepared glass sample had a transmittance of 48.9% to ultraviolet rays of 200 to 275nm wavelength band at a thickness of 2.0mm and a thermal expansion coefficient of 51.2X10 -7 and/C. Comparative example 5 uses the same total amount of single chloride instead of the chloride and graphite in example 1, and the prepared glass sample has a transmittance of 43.8% to ultraviolet rays of 200-275nm wavelength band at a thickness of 2.0mm and a thermal expansion coefficient of 51.3X10 -7 /℃。
In the ultraviolet-transmitting glass prepared in examples 1 to 18, the content of Fe impurity was 0.3 to 0.8ppm. In the glass samples prepared in comparative examples 1 to 3, the impurity Fe content was 35 to 41ppm. In the glass samples prepared in comparative examples 4 to 5, the content of Fe impurity was 28 to 32ppm. It can be seen that the method of the present invention can greatly reduce the content of Fe impurity in the ultraviolet ray transmitting glass, even by 2 orders of magnitude, as compared with comparative examples 1-3 and 4-5.
In the examples of the present invention (e.g., example 1) as compared with the above-described comparative examples, by reasonably adjusting the glass composition while introducing an impurity scavenger to reduce or remove the content of harmful impurities such as iron and the like in the glass and maintaining a certain degree of vacuum during the melting, a high-performance ultraviolet ray transmitting glass is obtained. The prepared ultraviolet-transmitting glass has a transmittance of 82.8% for ultraviolet rays in the 200-275nm band at a thickness of 2.0mm, and a thermal expansion coefficient of 50.5X10 -7 The optical performance is greatly improved at the temperature of/DEG C, and the thermal expansion coefficient and the kovar alloy are high in matching degree.
The technical features of the claims and/or the description of the present invention may be combined in a manner not limited to the combination of the claims by the relation of reference. The technical solutions obtained by combining the technical features in the claims and/or the description are also within the scope of the invention.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention in any way. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (12)
1. A method for producing an ultraviolet-transmitting glass, comprising:
mixing raw materials comprising the following components: 30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 Totaling 100wt%; and
adding impurity scavenger, melting under negative pressure to obtain the ultraviolet transmitting glass,
wherein the impurity scavenger comprises graphite and chloride.
2. The method according to claim 1, comprising the steps of:
1) Weighing the components in the raw materials according to the proportion, and mixing;
2) Adding the impurity scavenger to obtain a mixture;
3) Placing the mixture into a melting furnace, vacuumizing, and melting the mixture under negative pressure to obtain a glass melt;
4) And clarifying the glass melt, forming by material leakage, and annealing to obtain the ultraviolet-transmitting glass.
3. The method according to claim 2, wherein in step 2), the chloride is at least one selected from the group consisting of sodium chloride, potassium chloride, ammonium chloride, calcium chloride, and magnesium chloride.
4. The method according to claim 2, wherein in step 2) the graphite is used in an amount of 0.5-1.0wt% and the chloride is used in an amount of 0.3-0.8wt%, based on the total weight of the feedstock.
5. The method according to claim 2, wherein in step 3), the vacuum degree of the melting furnace is-0.05 MPa to-0.01 MPa.
6. The method according to claim 2, wherein in step 3), the melting temperature is 1450-1550 ℃ for 2-4h.
7. The method according to claim 2, wherein in step 4), the annealing is performed at a temperature of 490-530 ℃ for a time of 3-5 hours.
8. An ultraviolet-transmitting glass comprising, in terms of the components in the raw materials:30-50wt% of P 2 O 5 10-20wt% of SiO 2 5-10wt% of Al 2 O 3 10-20wt% of B 2 O 3 1-5wt% MgO,5-10wt% CaO,3-8wt% Li 2 O,2-8wt% of Y 2 O 3 And 2-8wt% of La 2 O 3 A total of 100wt%,
wherein, the raw material is added with an impurity scavenger containing graphite and chloride,
wherein, in the ultraviolet-transmitting glass, fe element as impurity is Fe 2 O 3 The content by weight is less than 1.0ppm based on the total weight of the ultraviolet-transmitting glass.
9. The ultraviolet-transmitting glass according to claim 8, wherein it is produced by the method according to any one of claims 1 to 7.
10. The ultraviolet-transmitting glass according to claim 9, wherein the ultraviolet-transmitting glass has a coefficient of thermal expansion of (50.+ -. 1). Times.10 -7 The transmittance of ultraviolet rays in the wavelength range of 200-275nm at the thickness of 2.0mm is more than 82 percent at the temperature of/DEG C.
11. An optical device comprising a high ultraviolet-transmitting window, a tube, or a camera lens, the high ultraviolet-transmitting window, tube, or camera lens comprising the ultraviolet-transmitting glass of any one of claims 8-10.
12. The optical device of claim 11, wherein the optical device is an ultraviolet detector, a large scale integrated circuit lithography, an ultraviolet optical lens, or an ultraviolet spectrometer.
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