CN112250303A - High-strength radiation-proof glass and preparation method and application thereof - Google Patents
High-strength radiation-proof glass and preparation method and application thereof Download PDFInfo
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- CN112250303A CN112250303A CN202011171901.9A CN202011171901A CN112250303A CN 112250303 A CN112250303 A CN 112250303A CN 202011171901 A CN202011171901 A CN 202011171901A CN 112250303 A CN112250303 A CN 112250303A
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- 239000011521 glass Substances 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 11
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 10
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims abstract description 8
- 229940075613 gadolinium oxide Drugs 0.000 claims abstract description 8
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003451 terbium oxide Inorganic materials 0.000 claims abstract description 8
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 8
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 6
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006060 molten glass Substances 0.000 claims description 83
- 238000001816 cooling Methods 0.000 claims description 37
- 230000005855 radiation Effects 0.000 claims description 36
- 238000000137 annealing Methods 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- 239000005347 annealed glass Substances 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 2
- 238000007493 shaping process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 9
- 238000005452 bending Methods 0.000 abstract description 9
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract description 8
- 230000005251 gamma ray Effects 0.000 abstract description 7
- 238000007496 glass forming Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 33
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 30
- 238000005728 strengthening Methods 0.000 description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 27
- 229910052726 zirconium Inorganic materials 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
- 235000010333 potassium nitrate Nutrition 0.000 description 11
- 239000004323 potassium nitrate Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000004017 vitrification 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
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
- C03B5/187—Stirring devices; Homogenisation with moving elements
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- 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
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
Abstract
The invention belongs to the technical field of special glass preparation, and particularly relates to high-strength radiation-proof glass and a preparation method and application thereof. The radiation-proof glass comprises silicon oxide, lead oxide, lithium oxide, sodium oxide, titanium oxide, zirconium oxide, yttrium oxide, terbium oxide, gadolinium oxide and antimony oxide. The invention is achieved by limiting the specific amounts of titanium dioxide, zirconium oxide and oxygenYttrium is formed, a stable chemical bond can be formed, the chemical stability of the glass is obviously improved, and the acid resistance stability can be improved to 1 level; adding lithium oxide and sodium oxide in specific quantity into glass, small radius ion (Li)2O and Na2O) exchanges with large-radius ions in the molten salt, so that the surface of the glass generates compressive stress, the bending strength and the glass forming property of the glass are improved, and the chemical stability of the glass is reduced due to the excessively high content of lithium oxide and sodium oxide; lead oxide, terbium oxide and gadolinium oxide are added into the glass, so that the gamma ray protection performance of the glass can be improved, and the ray shielding rate is ensured to be more than or equal to 99.01%.
Description
Technical Field
The invention belongs to the technical field of special glass preparation, and particularly relates to high-strength radiation-proof glass and a preparation method and application thereof.
Background
With the continuous development of science and technology, nuclear science and technology is increasingly widely applied in the fields of national defense, medicine, industry, agriculture, scientific research and the like. In the field of nuclear material preparation and nuclear science and technology applications, various radiations such as X-rays, gamma-rays and neutron radiations are extremely harmful to the human body, the environment, instruments and equipment, and are drawing great attention in the field of international radiation protection. Among the many rays, gamma rays have been the focus of radiation protection research because of their extreme permeability and hazardousness.
The inorganic transparent glass has the advantages of large adjustable range of components, good chemical stability, high mechanical strength and the like, and is an important transparent radiation-proof material. At present, typical products of radiation-proof glass are ZF series glass, such as ZF3, ZF6, ZF7 and other brands. ZF series glass has better gamma ray absorption capacity, but due to higher PbO content and untight glass network structure, the mechanical property of the glass is poorer, and the glass cannot be used for radiation-proof windows with special requirements. In order to improve the strength of the glass, the ZF series glass needs to be chemically toughened, but the ZF series glass has poor chemical stability and is very easy to be subjected to KNO3High-temperature lava corrosion, the transmittance is obviously reduced, and Li in ZF series glass2O and Na2The content of O is less than 1 wt%, which seriously restricts the strengthening effect of chemical tempering. Therefore, the improvement of the strength, chemical resistance and other performances of the existing radiation-proof glass has great difficulty.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor strength and chemical resistance and the like of the radiation-proof glass in the prior art, so that the high-strength radiation-proof glass and the preparation method and application thereof are provided.
Therefore, the invention provides the following technical scheme.
The invention provides high-strength radiation-proof glass which comprises, by mass, 20-40% of silicon oxide, 50-60% of lead oxide, 3-6% of lithium oxide, 1-3% of sodium oxide, 1-4% of titanium oxide, 1-4% of zirconium oxide, 1-4% of yttrium oxide, 1-6% of terbium oxide, 1-6% of gadolinium oxide and 0.2-1% of antimony oxide.
Further, the composite material comprises, by mass, 28-35% of silicon oxide, 55-60% of lead oxide, 3-5% of lithium oxide, 1-2% of sodium oxide, 1-2% of titanium oxide, 1-2% of zirconium oxide, 1-2% of yttrium oxide, 2-4% of terbium oxide, 1-3% of gadolinium oxide and 0.5-1% of antimony oxide.
The invention also provides a preparation method of the high-strength radiation-proof glass, which comprises the following steps,
the high-strength radiation-proof glass is obtained by uniformly mixing the raw materials, and carrying out high-temperature melting, forming, annealing and chemical toughening treatment.
The step of the chemical toughening treatment comprises the steps of placing the annealed glass in nitrate, heating to 360-420 ℃ at a heating rate of not more than 2 ℃/min, then carrying out chemical toughening treatment for 8-20h, and then cooling to room temperature at a cooling rate of not more than 2 ℃/min.
The nitrate is potassium nitrate and/or cesium nitrate;
when the nitrate is a mixture of potassium nitrate and cesium nitrate, the mass content of the cesium nitrate is more than or equal to 5%.
The melting method comprises the specific steps of placing the uniformly mixed raw materials at 1320-1450 ℃, and melting for 4-6h to form molten glass.
A further step of stirring the molten glass between said melting and forming steps until a clarified homogenized molten glass is formed;
the rotation speed of the stirring is 50-80 rpm.
In the melting process, the adopted melting device comprises a high-temperature melting furnace, a zirconium dispersion strengthening Pt crucible and a zirconium dispersion strengthening Pt stirrer; and stirring by adopting a zirconium dispersion strengthening Pt frame type stirrer for promoting clarification and homogenization of the molten glass, wherein the stirring time is 1-4 h.
The forming method specifically comprises the steps of cooling the glass liquid to 1100 ℃ of 1000 and placing the glass liquid in a mold at 400 ℃ of 320 and until the glass liquid is formed into a solid state.
The annealing temperature is 420-470 ℃, and the time is 4-6 h.
In addition, the invention also provides application of the high-strength radiation-proof glass or the high-strength radiation-proof glass prepared by the preparation method in the field of radiation protection of medical treatment, nuclear power or nuclear tests.
The high-strength radiation-proof glass is used for protecting gamma rays.
The technical scheme of the invention has the following advantages:
1. the high-strength radiation-proof glass provided by the invention comprises the components of silicon oxide, lead oxide, lithium oxide, sodium oxide, titanium oxide, zirconium oxide, yttrium oxide, terbium oxide, gadolinium oxide and antimony oxide. According to the invention, by limiting specific amounts of titanium dioxide, zirconium oxide and yttrium oxide, stable chemical bonds can be formed, the chemical stability of the glass is obviously improved, and the acid resistance stability can be improved to 1 level; adding lithium oxide and sodium oxide in specific quantity into glass, small radius ion (Li)2O and Na2O) exchanges with large-radius ions in the molten salt, so that the surface of the glass generates compressive stress, the bending strength and the glass forming property of the glass are improved, and the chemical stability of the glass is reduced due to the excessively high content of lithium oxide and sodium oxide; lead oxide, terbium oxide and gadolinium oxide are added into the glass, so that the gamma ray protection performance of the glass can be improved, and the ray shielding rate is ensured to be more than or equal to 99.01%.
Through the synergistic effect of the components, the radiation protection capability of the high-strength radiation protection glass can be ensured, the chemical stability, strength, transmittance and other performances of the glass can be improved, the bending strength of the glass is more than or equal to 136MPa, and the glass also has better gamma ray protection property, acid resistance and light transmittance, and is suitable for being used in the specific radiation protection fields of medical treatment, nuclear power, nuclear tests and the like.
2. The preparation method of the high-strength radiation-proof glass comprises the steps of uniformly mixing raw materials, forming after high-temperature melting, annealing and chemically toughening to obtain the high-strength radiation-proof glass. The invention can obviously improve the bending strength of the glass by carrying out the chemical toughening treatment step on the glass.
The bending strength of the radiation-proof glass is improved by controlling the chemical toughening treatment step. The heating rate and the cooling rate of the chemical toughening treatment step can be controlled to prevent the glass from cracking, the proper toughening treatment temperature is controlled to be favorable for improving the strength of the glass, the temperature is too high, the glass is easy to deform, the temperature is too low, and the toughening efficiency is lower.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at the temperature of 1320 ℃, melting for 5 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer after the batch forms molten glass, wherein the rotating speed is 80rpm, and the stirring time is 1 hour to form clarified and homogenized molten glass; cooling the molten glass to 1000 deg.C, and collectingPouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, naturally cooling the mold to form a solid state, then annealing the mold at 420 ℃ for 6 hours, turning off a power supply of an annealing furnace, naturally cooling the mold to room temperature, and then placing the mold on KNO3And (2) in the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1), heating to 360 ℃ at the heating rate of 2 ℃/min, carrying out chemical toughening treatment for 12h, and then, bringing the temperature to the room temperature at the rate of 2 ℃/min to obtain the high-strength radiation-proof glass.
Example 2
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at 1350 ℃, melting for 4 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer at the rotating speed of 50rpm for 2 hours after the batch forms molten glass to form clarified and homogenized molten glass; cooling the molten glass to 1050 ℃, pouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, naturally cooling the molten glass to form a solid state, annealing the solid state at 420 ℃ for 4 hours, turning off a power supply of an annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the solid state into KNO3And (2) heating the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1) at the heating rate of 2 ℃/min to 360 ℃ for chemical toughening treatment, wherein the chemical toughening treatment time is 20h, and then, cooling to room temperature at the speed of 2 ℃/min to obtain the high-strength radiation-proof glass.
Example 3
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, mixing to obtain batch, adding the batch to 1350 deg.CMelting for 6 hours in the zirconium dispersion strengthening Pt crucible, and after the glass liquid is formed by the ingredients, mechanically stirring by using a zirconium dispersion strengthening Pt stirrer at the rotating speed of 60rpm for 2 hours to form clarified and homogenized glass liquid; cooling the molten glass to 1000 ℃, pouring the homogenized molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 350 ℃, naturally cooling the molten glass to form a solid state, annealing the solid state at 420 ℃ for 5 hours, turning off a power supply of an annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the solid state into KNO3And (2) in the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1), heating to 360 ℃ at the heating rate of 2 ℃/min, carrying out chemical toughening treatment for 15h, and then, bringing the temperature to the room temperature at the speed of 2 ℃/min to obtain the high-strength radiation-proof glass.
Example 4
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a 1360 ℃ zirconium dispersion strengthening Pt crucible, melting for 4h, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer at the rotating speed of 50rpm for 1h after the batch forms molten glass to form clarified and homogenized molten glass; cooling the molten glass to 1000 ℃, pouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 350 ℃, annealing the molten glass at 440 ℃ for 4 hours after the molten glass is formed into a solid state, turning off a power supply of an annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the molten glass into KNO3In the molten salt, the temperature is raised to 360 ℃ at the heating rate of 2 ℃/min for chemical toughening treatment for 20h, and then the temperature is raised to the room temperature at the speed of 2 ℃/min, thus obtaining the high-strength radiation-proof glass.
Example 5
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a 1380 ℃ zirconium dispersion strengthening Pt crucible, melting for 4h, and after the batch forms molten glass, mechanically stirring by using a zirconium dispersion strengthening Pt stirrer at the rotating speed of 80rpm for 2h to form clarified and homogenized molten glass; cooling the molten glass to 1050 ℃, pouring the homogenized molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 360 ℃, annealing the molten glass at 440 ℃ for 6h after the molten glass is formed into a solid state, turning off a power supply of an annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the molten glass into KNO3And (2) heating the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 2:1) with the heating rate of 2 ℃/min to 380 ℃ for carrying out chemical toughening treatment for 8h, and then, returning to the room temperature with the heating rate of 2 ℃/min to obtain the high-strength radiation-proof glass.
Example 6
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at 1400 ℃, melting for 4 hours, forming glass liquid by the batch, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer at the rotating speed of 60rpm for 2 hours to form clarified and homogenized glass liquid; and cooling the molten glass to 1100 ℃, pouring the homogenized molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 360 ℃, annealing the preheated mold for 6 hours at 450 ℃ after the molten glass is formed into a solid state, turning off a power supply of an annealing furnace, naturally cooling the solid state to room temperature, placing the solid state into cesium nitrate molten salt, heating the solid state to 380 ℃ at a heating rate of 2 ℃/min for chemical toughening treatment for 15 hours, and then returning the solid state to the room temperature at a speed of 2 ℃/min to obtain the high-strength radiation-proof glass.
Example 7
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a 1450 ℃ zirconium dispersion strengthening Pt crucible, melting for 6 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer at the rotating speed of 50rpm for 1 hour after the batch forms molten glass to form clarified and homogenized molten glass; cooling the molten glass to 1100 ℃, pouring the homogenized molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 100 ℃, and waiting for the molten glass to form a solid state; then placing the mixture at 470 ℃ for annealing for 6h, turning off the power supply of the annealing furnace, naturally cooling the mixture to room temperature, and placing the mixture in KNO3And (2) heating the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1) with the heating rate of 2 ℃/min to 420 ℃ for chemical toughening treatment for 20h, and then, cooling to room temperature with the heating rate of 2 ℃/min to obtain the high-strength radiation-proof glass.
Example 8
This example provides a high strength radiation protective glass, with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at the temperature of 1320 ℃, melting for 5 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer after the batch forms molten glass, wherein the rotating speed is 80rpm, and the stirring time is 1 hour to form clarified and homogenized molten glass; cooling the molten glass to 1000 ℃, pouring the homogenized molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, annealing the preheated mold for 6 hours at 420 ℃ after the molten glass is formed into a solid state, turning off the power supply of the annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the annealed mold into KNO3Heating to 360 ℃ at the heating rate of 2 ℃/min in the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1) of cesium nitrate for chemical toughening treatment for 12h, and then cooling to room temperature at the speed of 2 ℃/min to obtain the high-strength radiation-proof composite materialAnd (3) glass.
Comparative example 1
The comparative example provides a high strength radiation protective glass with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at the temperature of 1320 ℃, melting for 5 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer after the batch forms molten glass, wherein the rotating speed is 80rpm, and the stirring time is 1 hour to form clarified and homogenized molten glass; and cooling the molten glass to 1000 ℃, pouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, annealing for 6 hours at 420 ℃ after the molten glass is naturally cooled to form a solid state, turning off a power supply of an annealing furnace, and naturally cooling to room temperature to obtain the high-strength radiation-proof glass.
Comparative example 2
The comparative example provides a high strength radiation protective glass with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at the temperature of 1320 ℃, melting for 5 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer after the batch forms molten glass, wherein the rotating speed is 80rpm, and the stirring time is 1 hour to form clarified and homogenized molten glass; cooling the molten glass to 1000 ℃, pouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, annealing the molten glass at 420 ℃ for 6 hours after the molten glass is formed into a solid state, turning off a power supply of the annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the molten glass into KNO3And (2) heating the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1) with the heating rate of 2 ℃/min to 360 ℃ for chemical toughening treatment for 12h, and then, cooling to room temperature with the heating rate of 2 ℃/min to obtain the high-strength radiation-proof glass.
Comparative example 3
The comparative example provides a high strength radiation protective glass with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at the temperature of 1320 ℃, melting for 5 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer after the batch forms molten glass, wherein the rotating speed is 80rpm, and the stirring time is 1 hour to form clarified and homogenized molten glass; cooling the molten glass to 1000 ℃, pouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, annealing the molten glass at 420 ℃ for 6 hours after the molten glass is formed into a solid state, turning off a power supply of the annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the molten glass into KNO3And (2) heating the mixed molten salt (the mass ratio of potassium nitrate to cesium nitrate is 1:1) with the heating rate of 2 ℃/min to 360 ℃ for chemical toughening treatment for 12h, and then, cooling to room temperature with the heating rate of 2 ℃/min to obtain the high-strength radiation-proof glass.
Comparative example 4
The comparative example provides a high strength radiation protective glass with the components and amounts referenced in table 1.
The preparation method of the high-strength radiation-proof glass comprises the following steps,
weighing raw materials, uniformly mixing to obtain a batch, adding the batch into a zirconium dispersion strengthening Pt crucible at the temperature of 1320 ℃, melting for 5 hours, and mechanically stirring by using a zirconium dispersion strengthening Pt stirrer after the batch forms molten glass, wherein the rotating speed is 80rpm, and the stirring time is 1 hour to form clarified and homogenized molten glass; cooling the molten glass to 1000 ℃, pouring the cooled molten glass into a preheated mold for forming in a pouring forming mode, wherein the temperature of the preheated mold is 320 ℃, annealing the molten glass at 420 ℃ for 6 hours after the molten glass is formed into a solid state, turning off a power supply of the annealing furnace, and naturally cooling the molten glass to room temperature, and then placing the molten glass into KNO3In the mixed molten salt with cesium nitrate (the mass ratio of potassium nitrate to cesium nitrate is 1:1), the temperature is raised to 360 ℃ at a temperature rise rate of 2 ℃/minCarrying out chemical toughening treatment for 12h, and then returning to room temperature at the speed of 2 ℃/min to obtain the high-strength radiation-proof glass.
TABLE 1 Components and amounts of radiation protective glasses obtained in examples 1 to 8 and comparative examples 1 to 4
Test examples
The test example provides the performance test and test method of the high-strength radiation-proof glass prepared in the examples 1 to 8 and the comparative examples 1 to 4, the test result is shown in the table 2, and the test method is as follows:
the method for testing the shielding rate of the high-strength radiation-proof glass comprises the following steps: using a radiation source of235U, radiation energy is 143KeV, the detector adopts high-purity germanium crystal, the sample is 10cm away from the radiation source and 10cm away from the detector, the radiation source is started to carry out gamma ray irradiation on the sample to be detected, the high-purity germanium detector is adopted to record energy spectrum, and the ray with energy of 143KeV is analyzed to analyze the totipotent peak area A under the condition of existence of the sample to be detectedIs provided withAnd ALight (es)And calculating the shielding rate (A)Light (es)-AIs provided with)/ALight (es)×100％。
The method for testing the acid resistance stability of the high-strength radiation-proof glass comprises the following steps: the tests were carried out according to the method of GB/T15728-1995 method for the gravimetric test and grading of the resistance of glass to boiling hydrochloric acid.
The method for testing the bending strength of the high-strength radiation-proof glass comprises the following steps: determination of the bending Strength of building glass, part 5, with reference to DIN EN 1288-5-2000: the test is carried out by the method of the small-area coaxial double-ring test on the surface of the plate glass sample.
The method for testing the transmittance of the high-strength radiation-proof glass comprises the following steps: the test is carried out according to the method of GB/T2680-.
TABLE 2 results of the Performance test of the glasses of examples 1 to 8 and comparative examples 1 to 4
As can be seen from Table 2, the radiation-proof glass prepared by the invention has good gamma ray resistance and acid resistance stability, and the bending strength of the toughened glass after chemical toughening is up to over 136 MPa.
Compared with the example 1, the radiation-proof glass of the comparative example 1 is not chemically toughened, and the bending strength is only 42 MPa; the radiation protective glass of comparative example 2 does not contain TiO2、ZrO2And Y2O3The oxide, such as glass, has poor acid resistance, and the transmittance is remarkably reduced after chemical tempering, so that the glass cannot be used as an optical window; the radiation protective glass of comparative example 3 does not contain Tb2O3And Gd2O3And the radiation protection capability of oxide and glass is poor, so that the radiation protection effect is difficult to effectively play.
The invention provides radiation-proof glass, SiO2The anti-radiation glass is an important network forming body, the glass forming capability, the strength and the chemical stability of the glass can be improved, but the melting temperature of the glass can be improved, and the difficulty is brought to the melting operation. In the embodiment of the invention, SiO2The weight percentage of the components is controlled to be 20-40%, preferably 28-35%, so that a homogeneous glass body can be obtained, and the reasonable melting temperature of the glass can be ensured. If the content of the component is less than 20% by weight, glass strength and chemical properties are deteriorated; if the content of the component exceeds 40% by weight, the glass has a high melting temperature, an increased viscosity and a deteriorated radiation-shielding ability.
PbO is a necessary component for the radiation protection capability of the glass provided by the invention, can improve the gamma ray absorption capability of the glass, and the weight percentage content of the component is controlled to be 50-60%, preferably 55-60%, so that a homogeneous glass body can be obtained, and the higher radiation protection performance of the glass can be ensured. If the weight percentage of the component is less than 50 percent, the radiation protection capability of the glass is poor, and the application requirement of special environment is difficult to meet; if the weight percentage of the component exceeds 60%, the mechanical property and chemical stability of the glass are poor, and chemical toughening is difficult.
Li2O is a component necessary for chemical toughening reinforcement of the radiation-proof glass, can provide alkali metal ions with small radius for a chemical toughening process, and realizes the purpose of realizing the purpose of mixing with metal ions (K) in high-temperature molten salt+、Cs+Etc.) to form compressive stress on the glass surface, thereby improving the glass strength. The invention controls the weight percentage of the component to be 3-6%, preferably 3-5%. If the weight percentage of the component is less than 3 percent, the enhancement and promotion effect on chemical toughening is not obvious; if the content of the component exceeds 6% by weight, the acid resistance of the glass is deteriorated.
Na2The mass percentage of O is controlled to be 1-3%, preferably 1-2%, which can not only promote the chemical toughening of the glass, but also ensure higher chemical performance. If the weight percentage of the component is less than 1 percent, the glass toughening strength is poor, and the application requirement of special environment is difficult to meet; if the content of the component exceeds 3% by weight, the acid resistance of the glass is deteriorated.
TiO2Is a component necessary for the radiation-proof glass to have excellent chemical stability, and the weight percentage of the component is controlled to be 1-4 percent, and the component is preferably 1-2 percent. If the weight percentage of the component is less than 1 percent, the chemical stability of the glass is not obviously improved; if the content of the component exceeds 4% by weight, TiO2Coloring will occur in the glass, reducing the glass transmittance.
ZrO2Is a component necessary for the radiation-proof glass to have excellent chemical stability, and the weight percentage of the component is controlled to be 1-4 percent, and the component is preferably 1-2 percent. If the weight percentage of the component is less than 1 percent, the chemical stability of the glass is not obviously improved; if the content of the component exceeds 4% by weight, ZrO2It is difficult to melt the glass sufficiently, and the optical uniformity of the glass is deteriorated.
Y2O3The radiation-proof glass is a necessary component with good chemical stability, and can promote the structural compactness of the glass and improve the acid resistance stability of the glass. The invention controls the mass content of the component to be 1-4%, preferably 1-2%. If the weight percentage of the component is less than 1 percent, the chemical stability of the glass is not obviously improved; if the content of this component exceeds 4% by weight, Y2O3It is difficult to sufficiently melt the glass, and the glass-forming property is deteriorated.
Tb2O3The components are beneficial to improving the glass forming performance and the radiation-proof performance of the radiation-proof glass. Tb2O3The weight percentage of the components is controlled to be 1-6%, preferably 2-4%. If Tb2O3The weight percentage of the components is less than 1 percent, the radiation protection and chemical stability of the glass are difficult to ensure, if Tb2O3When the weight percentage of the components exceeds 6%, the glass structure networking degree is reduced, and the glass vitrification is poor.
Gd2O3Function in radiation-proof glass and Tb2O3Similarly, the weight percentage of the components is controlled to be 1% -6%, preferably 1% -3%. If the weight percentage of the component is less than 1 percent, the radiation resistance and the chemical stability of the glass are poor, and the requirements of special environment application are difficult to meet; if the content of the component exceeds 6% by weight, the glass forming property of the glass is deteriorated and it is difficult to form a homogeneous body.
Sb2O3The component is used as a defoaming agent of radiation-proof glass, and the weight percentage of the component is controlled to be 0.2-1%, preferably 0.5-1%. If the weight percentage of the component is less than 0.2%, bubbles in the glass cannot be completely eliminated, and homogeneous glass cannot be obtained; if the content of the component exceeds 1% by weight, the excessive fining agent does not completely react, reducing the homogenizing effect of the glass.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The high-strength radiation-proof glass is characterized by comprising, by mass, 20-40% of silicon oxide, 50-60% of lead oxide, 3-6% of lithium oxide, 1-3% of sodium oxide, 1-4% of titanium oxide, 1-4% of zirconium oxide, 1-4% of yttrium oxide, 1-6% of terbium oxide, 1-6% of gadolinium oxide and 0.2-1% of antimony oxide.
2. The high-strength radiation-proof glass according to claim 1, wherein the composition comprises, by mass, 28 to 35% of silicon oxide, 55 to 60% of lead oxide, 3 to 5% of lithium oxide, 1 to 2% of sodium oxide, 1 to 2% of titanium oxide, 1 to 2% of zirconium oxide, 1 to 2% of yttrium oxide, 2 to 4% of terbium oxide, 1 to 3% of gadolinium oxide and 0.5 to 1% of antimony oxide.
3. The method for producing a high-strength radiation protective glass according to claim 1 or 2, comprising the steps of,
the high-strength radiation-proof glass is obtained by uniformly mixing the raw materials, and carrying out high-temperature melting, forming, annealing and chemical toughening treatment.
4. The method as claimed in claim 3, wherein the step of chemically tempering comprises placing the annealed glass in nitrate, raising the temperature to 360-420 ℃ at a temperature-raising rate of not more than 2 ℃/min, then chemically tempering for 8-20h, and then lowering the temperature to room temperature at a temperature-lowering rate of not more than 2 ℃/min.
5. The preparation method as claimed in claim 3 or 4, wherein the melting step comprises melting the uniformly mixed raw materials at 1320-1450 ℃ for 4-6h to form molten glass.
6. A method of making according to any of claims 3 to 5, further comprising the step of stirring the molten glass until a clarified homogenized molten glass is formed between the melting and forming steps;
the rotation speed of the stirring is 50-80 rpm.
7. The method as claimed in any one of claims 3-6, wherein the step of shaping comprises cooling the molten glass to 1100 ℃ at 1000 ℃ and placing the molten glass in a mold at 400 ℃ at 320 ℃ until the molten glass is solid.
8. The method as claimed in any one of claims 3 to 7, wherein the annealing temperature is 420 ℃ and 470 ℃ for 4 to 6 hours.
9. The high-strength radiation-proof glass of claim 1 or 2 or the high-strength radiation-proof glass prepared by the preparation method of any one of claims 3 to 8 is applied to the field of radiation protection of medical treatment, nuclear power or nuclear test.
10. Use according to claim 9, wherein the high-strength radiation-protective glass is used for protection against gamma rays.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876068A (en) * | 2021-03-26 | 2021-06-01 | 华南理工大学 | Gamma-ray irradiation darkening resistant germanate glass and preparation method and application thereof |
| CN112919802A (en) * | 2021-02-24 | 2021-06-08 | 河北省沙河玻璃技术研究院 | High-strength flexible radiation-resistant glass and preparation method thereof |
| CN113461325A (en) * | 2021-08-06 | 2021-10-01 | 中国建筑材料科学研究总院有限公司 | Aluminum-silicon glass and preparation method and application thereof |
| CN113979634A (en) * | 2021-12-02 | 2022-01-28 | 北方工业大学 | Novel X-ray radiation-proof special glass and preparation method thereof |
| CN114149177A (en) * | 2021-12-10 | 2022-03-08 | 江苏神盾新材料科技有限公司 | High-strength radiation-proof glass and preparation process thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4301057C1 (en) * | 1993-01-16 | 1994-03-31 | Schott Glaswerke | Reproducible cadmium@-free coloured glass useful in light display units - contg lead@ and oxide(s) of silicon, aluminium, germanium, zirconium, hafnium, titanium, tin, niobium, tantalum, etc |
| CN101928103A (en) * | 2009-06-23 | 2010-12-29 | 肖特公开股份有限公司 | Lead-containing space glass and preparation thereof and purposes |
| CN102503178A (en) * | 2011-10-24 | 2012-06-20 | 沈阳建筑大学 | Cesium-rubidium-potassium monolithic flameproof glass and preparation method |
| CN103597374A (en) * | 2011-03-29 | 2014-02-19 | 佐治亚技术研究公司 | Transparent glass scintillators, methods of making same and devices using same |
| CN103771708A (en) * | 2014-01-09 | 2014-05-07 | 秦皇岛星箭特种玻璃有限公司 | High-strength display screen glass |
| CN104291670A (en) * | 2013-07-19 | 2015-01-21 | 正达国际光电股份有限公司 | Glass treatment method |
| CN106007366A (en) * | 2016-07-20 | 2016-10-12 | 北京玻璃研究院 | Radiation shielding glass and preparation method thereof |
| CN106587596A (en) * | 2016-10-31 | 2017-04-26 | 中国科学院西安光学精密机械研究所 | Dense flint ZF series space irradiation resistant optical glass and preparation method thereof |
| CN107021621A (en) * | 2016-02-02 | 2017-08-08 | 肖特股份有限公司 | Shield X-ray and gamma-ray glass |
| CN108558201A (en) * | 2018-02-26 | 2018-09-21 | 中国建筑材料科学研究总院有限公司 | A kind of high ZrO2Content silicate glass and preparation method thereof |
| CN110937803A (en) * | 2019-12-27 | 2020-03-31 | 中建材蚌埠玻璃工业设计研究院有限公司 | Blue-light-proof high-strength aluminosilicate glass and preparation method thereof |
-
2020
- 2020-10-28 CN CN202011171901.9A patent/CN112250303A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4301057C1 (en) * | 1993-01-16 | 1994-03-31 | Schott Glaswerke | Reproducible cadmium@-free coloured glass useful in light display units - contg lead@ and oxide(s) of silicon, aluminium, germanium, zirconium, hafnium, titanium, tin, niobium, tantalum, etc |
| CN101928103A (en) * | 2009-06-23 | 2010-12-29 | 肖特公开股份有限公司 | Lead-containing space glass and preparation thereof and purposes |
| CN103597374A (en) * | 2011-03-29 | 2014-02-19 | 佐治亚技术研究公司 | Transparent glass scintillators, methods of making same and devices using same |
| CN102503178A (en) * | 2011-10-24 | 2012-06-20 | 沈阳建筑大学 | Cesium-rubidium-potassium monolithic flameproof glass and preparation method |
| CN104291670A (en) * | 2013-07-19 | 2015-01-21 | 正达国际光电股份有限公司 | Glass treatment method |
| CN103771708A (en) * | 2014-01-09 | 2014-05-07 | 秦皇岛星箭特种玻璃有限公司 | High-strength display screen glass |
| CN107021621A (en) * | 2016-02-02 | 2017-08-08 | 肖特股份有限公司 | Shield X-ray and gamma-ray glass |
| CN106007366A (en) * | 2016-07-20 | 2016-10-12 | 北京玻璃研究院 | Radiation shielding glass and preparation method thereof |
| CN106587596A (en) * | 2016-10-31 | 2017-04-26 | 中国科学院西安光学精密机械研究所 | Dense flint ZF series space irradiation resistant optical glass and preparation method thereof |
| CN108558201A (en) * | 2018-02-26 | 2018-09-21 | 中国建筑材料科学研究总院有限公司 | A kind of high ZrO2Content silicate glass and preparation method thereof |
| CN110937803A (en) * | 2019-12-27 | 2020-03-31 | 中建材蚌埠玻璃工业设计研究院有限公司 | Blue-light-proof high-strength aluminosilicate glass and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 田英良等: "《新编玻璃工艺学》", 30 June 2009 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919802A (en) * | 2021-02-24 | 2021-06-08 | 河北省沙河玻璃技术研究院 | High-strength flexible radiation-resistant glass and preparation method thereof |
| CN112876068A (en) * | 2021-03-26 | 2021-06-01 | 华南理工大学 | Gamma-ray irradiation darkening resistant germanate glass and preparation method and application thereof |
| CN113461325A (en) * | 2021-08-06 | 2021-10-01 | 中国建筑材料科学研究总院有限公司 | Aluminum-silicon glass and preparation method and application thereof |
| CN113979634A (en) * | 2021-12-02 | 2022-01-28 | 北方工业大学 | Novel X-ray radiation-proof special glass and preparation method thereof |
| CN114149177A (en) * | 2021-12-10 | 2022-03-08 | 江苏神盾新材料科技有限公司 | High-strength radiation-proof glass and preparation process thereof |
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