CN111116041A - Ultraviolet band high-transmittance anti-radiation optical glass and preparation method thereof - Google Patents
Ultraviolet band high-transmittance anti-radiation optical glass and preparation method thereof Download PDFInfo
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- CN111116041A CN111116041A CN201911352309.6A CN201911352309A CN111116041A CN 111116041 A CN111116041 A CN 111116041A CN 201911352309 A CN201911352309 A CN 201911352309A CN 111116041 A CN111116041 A CN 111116041A
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- 238000002834 transmittance Methods 0.000 title claims abstract description 69
- 239000005304 optical glass Substances 0.000 title claims abstract description 39
- 230000003471 anti-radiation Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 230000005855 radiation Effects 0.000 claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 29
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000003086 colorant Substances 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 15
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims abstract description 13
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims abstract description 13
- 229960001633 lanthanum carbonate Drugs 0.000 claims abstract description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000011975 tartaric acid Substances 0.000 claims description 10
- 235000002906 tartaric acid Nutrition 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims 2
- 239000011521 glass Substances 0.000 abstract description 85
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000008859 change Effects 0.000 abstract description 2
- 230000002285 radioactive effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000005365 phosphate glass Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910016287 MxOy Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- RKVCQBPDVHFKCU-UHFFFAOYSA-N 2,4,5-trioxa-1$l^{5}-phospha-3-borabicyclo[1.1.1]pentane 1-oxide Chemical compound O1B2OP1(=O)O2 RKVCQBPDVHFKCU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MRHPUNCYMXRSMA-UHFFFAOYSA-N nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Ni++] MRHPUNCYMXRSMA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured 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
- C03C4/08—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
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)
- Glass Compositions (AREA)
Abstract
The invention provides ultraviolet band high-transmittance anti-radiation optical glass and a preparation method thereof, wherein the ultraviolet band high-transmittance anti-radiation optical glass comprises the following components in parts by weight: 60-70 parts of phosphoric acid, 13-15 parts of boric acid, 8-12 parts of aluminum oxide, 4-6 parts of barium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 0.8-1.8 parts of a coloring agent A1, 2.8-2.8 parts of a coloring agent B2, 0.5-1 part of a reducing agent and 0.5-1 part of a stabilizing agent. The optical glass improves the high transmittance and radiation resistance of ultraviolet band by changing the glass composition and structure, is not easy to change color after absorbing strong radioactive rays, and solves the technical problems that the current peak transmittance of the ultraviolet glass in the ultraviolet band is only about 80 percent, and the current practical application requirement needs to reach more than 85 percent.
Description
Technical Field
The invention relates to glass for medical fluorescence detection equipment, in particular to optical glass with high ultraviolet band transmittance and ultraviolet irradiation resistance.
Background
Glass mainly comprises two major categories of plate glass and deep processing glass, wherein the plate glass mainly comprises three types: flat glass by the drawing method (divided into a grooved glass and a non-grooved glass), flat glass by the flat drawing method, and float glass. The deep processing glass is made of plate glass, and has a wide application range. The ultraviolet high-transmittance optical glass refers to optical glass which has the same optical constants and physical and chemical properties as certain colorless optical glass, but has much higher transmittance of ultraviolet light and visible light than general optical glass. The ultraviolet spectrometer is mainly used for ultraviolet spectrometers and photoelectric devices, and optical instruments, camera lenses and the like which require high visible light transmittance.
Factors affecting the ultraviolet transmittance of the glass other thanDepending on impurities in the glass, e.g. Fe, in addition to the chemical composition of the glass matrix3+，Mn2+，Ce4+，Ti4+And plasma impurity ions. Therefore, high-purity raw materials are selected for producing the ultraviolet high-transmittance optical glass, and contamination is prevented during melting.
The radiation-resistant glass is one of the broad optical glasses. Including radiation-resistant glass and radiation-resistant glass. Radiation-proof glass is mainly glass with large absorption capacity to gamma rays and X rays. When gamma rays or X rays enter the protective glass, because the photoelectric effect is generated in the glass, positive and negative electron pairs are generated, and excited state electrons and free state electrons are generated at the same time, the energy of the incident gamma rays or X rays is reduced, the penetrating power is reduced, and the protective effect is achieved. The composition of ordinary glass cannot absorb such rays effectively, and a large amount of elements with high atomic numbers (such as lead and bismuth) must be introduced into the glass composition to improve the absorption capacity. In addition, since the glass itself tends to turn dark brown and lose transparency after absorbing strong radiation, the glass itself is also required to have high radiation resistance.
How to combine two functions, namely glass which can be penetrated by ultraviolet rays and can resist radiation, is important for research and development, and the application range of the glass can be expanded.
The invention provides a novel optical glass material, which enables ultraviolet glass to have high transmittance in an ultraviolet band and simultaneously have the functions of radiation resistance and aging resistance.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide ultraviolet band high-transmittance anti-radiation optical glass and a preparation method thereof, which improve the transmittance of the ultraviolet glass in an ultraviolet band and enable the ultraviolet glass to have a good anti-radiation function.
The technical scheme is as follows: in order to achieve the purpose, the invention provides the following technical scheme:
the invention relates to ultraviolet band high-transmittance anti-radiation optical glass which comprises the following components in parts by weight:
60-70 parts of phosphoric acid, 13-15 parts of boric acid, 8-12 parts of aluminum oxide, 4-6 parts of barium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 0.8-1.8 parts of a coloring agent A1, 2.8-2.8 parts of a coloring agent B2, 0.5-1 part of a reducing agent and 0.5-1 part of a stabilizing agent.
Preferably, 60-65 parts of phosphoric acid, 13-14 parts of boric acid, 10 parts of aluminum oxide, 5 parts of barium carbonate, 5 parts of potassium carbonate, 3.5-4 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 1.5 parts of a coloring agent A, 2.3 parts of a coloring agent B, 0.7 part of a reducing agent and 0.7 part of a stabilizing agent.
Preferably, the stabilizer is ceria and strontium oxide, with the strontium oxide to ceria ratio being 2: 1.
Preferably, the colorant A is cobalt oxide, the colorant B is nickel oxide, and the ratio of nickel oxide to cobalt oxide is 1: 2.
Preferably, the reducing agent is tartaric acid and silica in a 2:1 ratio.
The preparation method of the ultraviolet band high-transmittance anti-radiation optical glass comprises the following steps:
step one, uniformly mixing raw materials; the raw materials comprise the following components in parts by weight:
60-70 parts of phosphoric acid, 13-15 parts of boric acid, 8-12 parts of aluminum oxide, 4-6 parts of barium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 1-1.8 parts of cobalt oxide, 2-2.8 parts of nickel oxide, 0.5-1 part of reducing agent and 0.5-1 part of stabilizing agent;
step two, after the material feeding is finished, heating to the temperature of 1100-1500 ℃, wherein the heating time is 0.5-1.5 hours; the melting temperature is 1100 ℃ and 1500 ℃, and the melting time lasts for 4 hours; cooling from 1100-1300 ℃ to 1000-1300 ℃, wherein the cooling time is 1 hour, and the discharging temperature is 1000-1300 ℃; and annealing, wherein the temperature is reduced at 600 ℃ in 400-.
Preferably, after the feeding is finished, the temperature is raised to 1330 ℃, and the temperature rise time is 1 hour; the melting temperature was 1330 ℃ for 4 hours; cooling from 1330 ℃ to 1160 ℃, wherein the cooling time is 1 hour, and the discharging temperature is 1160 ℃; annealing, cooling to 560 ℃ per hour at 10 ℃, and closing the power to naturally cool when the temperature is reduced to 300 ℃.
Phosphoric acid is a main component of glass in the present invention. Because ultraviolet glass needs to transmit short-wave-band ultraviolet glass, a phosphate glass system is selected: i.e. P2O5-AL2O3-B2O3A glass system; meanwhile, the ultraviolet glass needs to be cut off in the visible light part, so that the coloring agent adopts nickel, and the introduction of nickel ions can not influence the transmission of the ultraviolet light while cutting off the visible light. And at P2O5-AL2O3-B2O3In the glass system, the content of alkali metal oxide is less, and nickel ions are mainly in hexacoordination [ NiO6]The nickel ions have high transmittance in the ultraviolet part, and the transmittance range also shifts to the ultraviolet short wave direction, so that the glass system with a phosphate structure is comprehensively considered. The components are controlled to be 60 to 70 parts by weight, and the best is 60 to 65 parts by weight.
Boric acid is an important component of the phosphate structured glass system of the present invention. The disadvantage of poor chemical stability of phosphate glass can be improved by adding boric acid. Meanwhile, boric acid is a good fluxing agent, and can lower the melting point of glass. The boric acid is too much to cause "boron abnormality" and is not easily excessively introduced, so that the composition is controlled to 13 to 15 parts by weight, preferably 13 to 14 parts by weight.
Alumina in the present invention forms aluminum orthophosphate (Al) with phosphoric acid and boric acid as part of the phosphate glass architecture2O3·P2O5) With boron orthophosphate (B)2O3·P2O5) Due to glass formation of AlPO4And BPO4The original layered structure of the phosphate is changed into a frame structure, so that the chemical stability of the phosphate glass is improved, and the thermal expansion coefficient is reduced. The component accounts for 8 to 12 weight parts, and the best component accounts for 10 weight parts.
Cobalt oxide is used as one of the colorants of the glass of the present invention, and serves to cut off the visible light band in combination with nickel, which is another colorant. Cobalt ion is hexa-coordinated [ NiO ] in phosphate glass6]There is a strong absorption mainly at 550 nm. The components are 1-1.8 parts by weight, preferably 1.5 parts by weight;
barium carbonate in the invention mainly acts as a flux and increases the density and strength of the glass; the component is 4-6 weight parts, preferably 5 weight parts;
the potassium carbonate in the invention mainly plays a role in breaking a net in glass, and can improve the chemical stability, surface tension and crystallization capacity of the glass. The component is 4-6 weight parts, preferably 5 weight parts;
calcium carbonate in the present invention is a divalent metal oxide. The calcium ions have the effects of polarizing bridge oxygen and weakening silicon-oxygen bonds, so that the high-temperature viscosity of the glass can be reduced, meanwhile, non-bridge oxygen is reduced, and the phenomenon that free electrons generated by ionizing radiation are captured by the non-bridge oxygen, so that the ultraviolet band absorption is caused, and the transmittance of the glass in the ultraviolet band is declined is avoided. However, since too much increases brittleness of the glass and is liable to devitrify, the composition is controlled to 3 to 5 parts by weight, preferably 3.5 to 4 parts by weight.
The nickel oxide is used as a coloring agent of the glass and is matched with another coloring agent cobalt for use, and the purpose of the nickel oxide is to cut off a visible light wave band. The nickel ions are mainly [ NiO ] in the phosphate glass6]There is a strong absorption at 430 nm. However, when the amount of the nickel is too large, the transmittance peak shifts from 430nm to a short wavelength, which is extremely disadvantageous for ultraviolet-transmitting glass, and therefore, it is preferable to incorporate 2 to 2.8 parts by weight of nickel, and the most preferable amount is 2.3 parts by weight, and it is also necessary to incorporate cobalt in an appropriate ratio, and the most preferable ratio of nickel to cobalt is 1: 2.
In the invention, the mixture of tartaric acid and silicon dioxide is used as a reducing agent of the glass, and in order to solve the problems of low ultraviolet band transmittance and radiation resistance, a proper amount of reducing agent is added into the formula of the glass, because trace impurity Fe3+ is inevitably present in the glass raw material, thereby affecting the ultraviolet transmittance. In order to improve the transmittance of ultraviolet bands, a proper reducing agent tartaric acid is introduced, and the impurity Fe3+ is reduced, so that the ultraviolet absorption is reduced, and the ultraviolet transmittance is improved.
The main components of the stabilizing agent in the invention are cerium dioxide and strontium oxide; the stabilizer mainly improves the transmittance reduction of the ultraviolet glass due to long-term irradiation. The current principle about the reason of ultraviolet glass aging is basically clarified: because electron radiation generates free electrons or positive holes, the free electrons or the positive holes are captured by non-bridging oxygen and interstitial atoms to form a new electronic structure, and then absorption is generated in an ultraviolet band, so that the ultraviolet transmittance is reduced. The reason for selecting strontium oxide in the glass stabilizer is that the strontium oxide has strong electric field intensity, belongs to a network exo-oxide and plays a role in gathering non-bridge oxygen, thereby reducing the non-bridge oxygen and improving the defects of the internal structure of the glass. And cerium dioxide as a hole trapping substance can compete with the valence-variable oxide of the glass, so that the hole is trapped firstly, and the structural defect of the glass or valence-variable ions are difficult to trap the positive hole. However, excessive strontium oxide can cause the glass to be too compact and easy to crystallize; while an excessive amount of cerium oxide causes coloring, which affects ultraviolet transmittance. Therefore, the amount of the stabilizer is preferably 0.5 to 1 part by weight, more preferably 0.7 part by weight. Wherein the ratio of strontium oxide to cerium oxide in the stabilizer is preferably 2: 1.
Has the advantages that: by adopting the technical scheme, compared with the prior art, the invention has the following advantages:
1. the optical glass adopts a phosphoric acid system, and comprises the following components: boric acid, aluminum oxide, barium carbonate, potassium carbonate, calcium carbonate and lanthanum carbonate, and in order to ensure that high-transmittance and radiation-resistant ultraviolet-transmitting glass is obtained, a reducing agent is required to be introduced into the glass batch to ensure the transmittance and radiation resistance of the ultraviolet-transmitting glass. The invention adjusts the components of the glass and improves the internal structure of the glass. Thereby finally providing the glass with a durable radiation-resistant function. The technical problem of aging phenomenon caused by continuous reduction of the transmittance of ultraviolet bands of the ultraviolet glass due to long-time ultraviolet radiation of the ultraviolet glass at present is solved. The invention ensures the ultraviolet radiation resistance and does not influence the spectral performance of the glass.
2. The optical glass improves the high transmittance and radiation resistance of ultraviolet band by changing the glass composition and structure, is not easy to change color after absorbing strong radioactive rays, and solves the technical problems that the current peak transmittance of the ultraviolet glass in the ultraviolet band is only about 80 percent, and the current practical application requirement needs to reach more than 85 percent. The application range of the optical glass is greatly expanded.
3 the peak transmittance of the optical glass in the ultraviolet band reaches 90%, and the average transmittance of visible light between 450nm and 650nm is 0.13%, so that the effect of cut-off is achieved. The glass has an ultraviolet transmission reduction rate of 1.45 percent and excellent radiation resistance.
Detailed Description
The invention relates to ultraviolet band high-transmittance anti-radiation optical glass which comprises the following components in parts by weight:
P2O560-70 parts of phosphoric acid, B2O313-15 parts of boric acid, Al2O38-12 parts of alumina, BaCO34-6 parts of barium carbonate, K2CO34-6 parts of potassium carbonate, CaCO33-5 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 1-1.8 parts of cobalt oxide, 2-2.8 parts of nickel oxide, 0.5-1 part of tartaric acid and 0.5-1 part of stabilizer.
The stabilizing agent is cerium dioxide and strontium oxide, and the ratio of the strontium dioxide to the cerium oxide is 2: 1. The ratio of nickel dioxide to cobalt oxide is 1: 2.
In order that the objects, aspects and advantages of the invention will become more apparent, the invention is described below by way of specific examples. It is to be understood that such description is merely illustrative and not restrictive of the scope of the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
In the embodiment of the invention, all raw materials are AR grade, so that the iron-containing impurities in the raw materials are reduced to the maximum extent, and the ultraviolet transmittance of the glass is influenced. After purchasing the AR grade material, the purification is performed again in the factory. The melting crucible and the blade paddle adopt quartz crucibles, and the quartz crucibles are selected to prevent iron impurities from polluting raw materials.
Example 1
In this embodiment, the ultraviolet-band high-transmittance radiation-resistant optical glass comprises the following components in parts by weight:
60 parts of phosphoric acid, 13 parts of boric acid, 8 parts of alumina, 4 parts of barium carbonate, 4 parts of potassium carbonate, 3 parts of calcium carbonate, 0.5 part of lanthanum carbonate, 1 part of cobalt oxide, 2 parts of nickel oxide, 0.5 part of a mixture of tartaric acid and silicon dioxide, 0.5 part of cerium oxide and 0.25 part of strontium oxide.
Uniformly mixing the raw materials, heating to 1330 ℃, wherein the heating time is 1 hour; the melting temperature was 1330 ℃ for 4 hours. The temperature is reduced from 1330 ℃ to 1160 ℃, the temperature reduction time is 1 hour, and the discharging temperature is about 1160 ℃. And (3) final annealing, cooling at 560 ℃, and naturally cooling at 10 ℃ per hour after electricity is cut off to 300 ℃ to obtain the optical glass with high ultraviolet band transmittance and ultraviolet radiation resistance.
Testing the spectrum of the ultraviolet glass by a spectrophotometer according to the national standard GB/T15489.1: sample standard test thickness 1mm, sample transmittance at different wavelengths: 313nm is more than 89%; 334nm is more than 90 percent; 405nm is less than 17.5 percent; 700nm is less than 59.1%; the average transmittance of 450nm-650nm is less than 0.13 percent.
Example 2
In this embodiment, the ultraviolet-band high-transmittance radiation-resistant optical glass comprises the following components in parts by weight:
65 parts of phosphoric acid, 14 parts of boric acid, 10 parts of alumina, 5 parts of barium carbonate, 5 parts of potassium carbonate, 4 parts of calcium carbonate, 0.5 part of lanthanum carbonate, 1.5 parts of cobalt oxide, 2.5 parts of nickel oxide, 0.8 part of a mixture of tartaric acid and silicon dioxide, 0.6 part of cerium oxide and 0.3 part of strontium oxide.
Uniformly mixing the raw materials, heating to 1330 ℃, wherein the heating time is 1 hour; the melting temperature was 1330 ℃ for 4 hours. The temperature is reduced from 1330 ℃ to 1160 ℃, the temperature reduction time is 1 hour, and the discharging temperature is about 1160 ℃. And (3) final annealing, cooling at 560 ℃, and naturally cooling at 10 ℃ per hour after electricity is cut off to 300 ℃ to obtain the optical glass with high ultraviolet band transmittance and ultraviolet radiation resistance.
Testing the spectrum of the ultraviolet glass by a spectrophotometer according to the national standard GB/T15489.1: sample standard test thickness 1mm, sample transmittance at different wavelengths: 313nm is more than 90 percent; 334nm is more than 91 percent; 405nm is less than 16.5 percent; 700nm is less than 58.1 percent; the average transmittance of 450nm-650nm is less than 0.12 percent.
Example 3
In this embodiment, the ultraviolet-band high-transmittance radiation-resistant optical glass comprises the following components in parts by weight:
70 parts of phosphoric acid, 15 parts of boric acid, 12 parts of alumina, 6 parts of barium carbonate, 6 parts of potassium carbonate, 5 parts of calcium carbonate, 1 part of lanthanum carbonate, 1.8 parts of cobalt oxide, 2.8 parts of nickel oxide, 1 part of a mixture of tartaric acid and silicon dioxide, 0.7 part of cerium oxide and 0.3 part of strontium oxide.
Uniformly mixing the raw materials, heating to 1330 ℃, wherein the heating time is 1 hour; the melting temperature was 1330 ℃ for 4 hours. The temperature is reduced from 1330 ℃ to 1160 ℃, the temperature reduction time is 1 hour, and the discharging temperature is about 1160 ℃. And (3) final annealing, cooling at 560 ℃, and naturally cooling at 10 ℃ per hour after electricity is cut off to 300 ℃ to obtain the optical glass with high ultraviolet band transmittance and ultraviolet radiation resistance.
Comparative example 1
Comparative example 1 differs from example 1 in that: the components in comparative example 1 in parts by weight: 60 parts of phosphoric acid, 13 parts of boric acid, 8 parts of alumina, 4 parts of barium carbonate, 4 parts of potassium carbonate and 3 parts of calcium carbonate.
The ultraviolet band high-transmittance radiation-resistant optical glass obtained in the above examples 1 to 3 was used for testing the spectrum of ultraviolet glass by a spectrophotometer according to the national standard GB/T15489.1: sample standard test thickness 1mm, sample transmittance at different wavelengths: 313nm is more than 90 percent; 334nm is more than 91 percent; 405nm is less than 16.5 percent; 700nm is less than 58.1 percent; the average transmittance of 450nm-650nm is less than 0.12 percent.
The ultraviolet resistance of the ultraviolet band high-transmittance radiation-resistant optical glass of the present invention will be tested.
Sample testing method
1. Testing the ultraviolet glass spectrum by a spectrophotometer: the standard test thickness of the sample is 1mm, and the national standard GB/T15489.1 spectrum test method is adopted.
Table 1 shows the measurement results of the transmittance of the optical glass of the present invention with high transmittance in the ultraviolet band and ultraviolet radiation resistance at different wavelengths.
Table 1 transmittance of ultraviolet band high transmittance and ultraviolet irradiation resistant optical glass at different wavelengths:
| serial number | Wavelength (nm) | Transmittance (%) |
| 1 | 313nm | 89.91 |
| 2 | 334nm | 90.12 |
| 3 | 405nm | 17.5 |
| 4 | 700nm | 59.1 |
| 5 | Average transmittance of 450- | 0.13 |
As can be seen from the data in Table 1, the ultraviolet-transmitting glass has good ultraviolet-transmitting performance, the peak value reaches 90.12%, the average transmittance of visible light between 450nm and 650nm is only 0.13%, and the effect of visible light cut-off is achieved.
The ultraviolet resistance performance of the optical glass with high ultraviolet band transmittance and ultraviolet radiation resistance of the invention is tested.
2. Calculation of test results
The radiation protection of glass depends primarily on its ability to absorb radiation energy. Classical theory holds that the absorption capacity of a glass for high energy radiation energy can be calculated as follows:
I＝I0e-μl
μ＝ω ρ
in the formula: i is0The initial ray intensity and the ray intensity after passing through the glass; t is the glass thickness; u is the absorption coefficient of the narrow ray; rho is the glass density; field glass absorption coefficient; f. ofMxOyIs the mass percentage of each component oxide in the glass; omega MxOyIs the mass absorption coefficient of each oxide in the glass composition.
Table 2 compares the radiation protection capabilities:
as can be seen from the above table, the radiation protection capability of the glass can be increased by changing the composition and structure of the glass. The glass containing lanthanum carbonate has lower density but can generate better radiation protection effect. The structural network is the most compact when the ratio of tartaric acid to silica is 2: 1.
The peak transmittance of the product in the ultraviolet band reaches 90%, the product meets the high transmittance performance in the ultraviolet band, the average transmittance of the visible light is 0.13% between 450nm and 650nm, and the effect of cut-off is achieved. Through an ultraviolet irradiation experiment, the glass has the ultraviolet transmission reduction rate of 2.35 percent and has excellent ultraviolet ageing resistance and radiation resistance.
Claims (7)
1. The ultraviolet band high-transmittance anti-radiation optical glass is characterized by comprising the following components in parts by weight:
60-70 parts of phosphoric acid, 13-15 parts of boric acid, 8-12 parts of aluminum oxide, 4-6 parts of barium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 0.8-1.8 parts of a coloring agent A1, 2.8-2.8 parts of a coloring agent B2, 0.5-1 part of a reducing agent and 0.5-1 part of a stabilizing agent.
2. The ultraviolet band high-transmittance radiation-resistant optical glass according to claim 1, which is characterized by comprising the following components in parts by weight:
60-65 parts of phosphoric acid, 13-14 parts of boric acid, 10 parts of aluminum oxide, 5 parts of barium carbonate, 5 parts of potassium carbonate, 3.5-4 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 1.5 parts of a coloring agent A, 2.3 parts of a coloring agent B, 0.7 part of a reducing agent and 0.7 part of a stabilizing agent.
3. The ultraviolet band high-transmittance radiation-resistant optical glass according to claim 1 or 2, wherein the stabilizer is cerium oxide and strontium oxide, and the ratio of strontium oxide to cerium oxide is 2: 1.
4. The ultraviolet band high-transmittance radiation-resistant optical glass according to claim 1 or 2, wherein the colorant A is cobalt oxide, the colorant B is nickel oxide, and the ratio of nickel oxide to cobalt oxide is 1: 2.
5. The ultraviolet band high-transmittance radiation-resistant optical glass according to claim 1, wherein the reducing agent is tartaric acid and silica, and the ratio of tartaric acid to silica is 2: 1.
6. The method for preparing the ultraviolet band high-transmittance radiation-resistant optical glass according to claim 1, characterized by comprising the following steps:
step one, uniformly mixing raw materials; the raw materials comprise the following components in parts by weight:
60-70 parts of phosphoric acid, 13-15 parts of boric acid, 8-12 parts of aluminum oxide, 4-6 parts of barium carbonate, 4-6 parts of potassium carbonate, 3-5 parts of calcium carbonate, 0.5-1 part of lanthanum carbonate, 1-1.8 parts of cobalt oxide, 2-2.8 parts of nickel oxide, 0.5-1 part of reducing agent and 0.5-1 part of stabilizing agent;
step two, after the material feeding is finished, heating to the temperature of 1100-1500 ℃, wherein the heating time is 0.5-1.5 hours; the smelting temperature is 1100-1500 ℃, and the smelting lasts for 4 hours; cooling from 1100-1300 ℃ to 1000-1300 ℃, wherein the cooling time is 1 hour, and the discharging temperature is 1000-1300 ℃; annealing, cooling at the temperature of 600 ℃ in 400-.
7. The method for preparing the ultraviolet band high-transmittance radiation-resistant optical glass as claimed in claim 1, which is characterized in that the temperature is raised to 1330 ℃ after the charging is finished, and the temperature is raised for 1 hour; the melting temperature was 1330 ℃ for 4 hours; cooling from 1330 ℃ to 1160 ℃, wherein the cooling time is 1 hour, and the discharging temperature is 1160 ℃; annealing, cooling to 560 ℃ per hour at 10 ℃, and closing the power to naturally cool when the temperature is reduced to 300 ℃.
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| CN201911352309.6A CN111116041A (en) | 2019-12-25 | 2019-12-25 | Ultraviolet band high-transmittance anti-radiation optical glass and preparation method thereof |
| PCT/CN2020/084565 WO2021128656A1 (en) | 2019-12-25 | 2020-04-13 | Ultraviolet band high-transmittance and anti-radiation optical glass and preparation method therefor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825334A (en) * | 2020-06-16 | 2020-10-27 | 驻马店市辉源照明器材有限公司 | Ultraviolet-transmitting high-boron glass tube and preparation method thereof |
| CN114180832A (en) * | 2021-11-29 | 2022-03-15 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant and medium wave infrared glass and preparation method and application thereof |
| CN116573857A (en) * | 2023-07-12 | 2023-08-11 | 山东龙光天旭太阳能有限公司 | Borosilicate glass with high ultraviolet transmittance and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3242513A1 (en) * | 1982-11-18 | 1984-06-07 | Schott Glaswerke, 6500 Mainz | Alkali metal or alkaline-earth metal phosphate glasses with substantially reduced solarisation tendency for optical coloured and filter glasses |
| US4615989A (en) * | 1984-04-18 | 1986-10-07 | Schott Glaswerke | Optical quality colored glass |
| US20130105744A1 (en) * | 2010-04-23 | 2013-05-02 | Asahi Glass Company, Limited | Ultraviolet transmitting near infrared cut filter glass |
| CN106966590A (en) * | 2017-05-18 | 2017-07-21 | 南通市国光光学玻璃有限公司 | The preparation method of the optical glass of ultraviolet band high transmission and resistance to ultraviolet irradiation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5108959A (en) * | 1990-11-16 | 1992-04-28 | Lockheed Missiles & Space Company, Inc. | Terbium activated borate luminescent glasses coactivated with gadolinium oxide |
-
2019
- 2019-12-25 CN CN201911352309.6A patent/CN111116041A/en active Pending
-
2020
- 2020-04-13 WO PCT/CN2020/084565 patent/WO2021128656A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3242513A1 (en) * | 1982-11-18 | 1984-06-07 | Schott Glaswerke, 6500 Mainz | Alkali metal or alkaline-earth metal phosphate glasses with substantially reduced solarisation tendency for optical coloured and filter glasses |
| US4615989A (en) * | 1984-04-18 | 1986-10-07 | Schott Glaswerke | Optical quality colored glass |
| US20130105744A1 (en) * | 2010-04-23 | 2013-05-02 | Asahi Glass Company, Limited | Ultraviolet transmitting near infrared cut filter glass |
| CN106966590A (en) * | 2017-05-18 | 2017-07-21 | 南通市国光光学玻璃有限公司 | The preparation method of the optical glass of ultraviolet band high transmission and resistance to ultraviolet irradiation |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825334A (en) * | 2020-06-16 | 2020-10-27 | 驻马店市辉源照明器材有限公司 | Ultraviolet-transmitting high-boron glass tube and preparation method thereof |
| CN114180832A (en) * | 2021-11-29 | 2022-03-15 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant and medium wave infrared glass and preparation method and application thereof |
| CN114180832B (en) * | 2021-11-29 | 2023-09-29 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant intermediate wave transparent infrared glass and preparation method and application thereof |
| CN116573857A (en) * | 2023-07-12 | 2023-08-11 | 山东龙光天旭太阳能有限公司 | Borosilicate glass with high ultraviolet transmittance and preparation method thereof |
| CN116573857B (en) * | 2023-07-12 | 2023-10-27 | 山东龙光天旭太阳能有限公司 | Borosilicate glass with high ultraviolet transmittance and preparation method thereof |
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