CN112250298B - Radiation-proof glass and preparation method and application thereof - Google Patents
Radiation-proof glass and preparation method and application thereof Download PDFInfo
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- CN112250298B CN112250298B CN202011176019.3A CN202011176019A CN112250298B CN 112250298 B CN112250298 B CN 112250298B CN 202011176019 A CN202011176019 A CN 202011176019A CN 112250298 B CN112250298 B CN 112250298B
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/02—Annealing glass products in a discontinuous way
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- 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
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- 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
- C03B5/2353—Heating the glass by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention belongs to the technical field of special glass preparation, and particularly relates to radiation-proof glass and a preparation method and application thereof. The radiation-proof glass comprises silicon oxide, lanthanum oxide, gadolinium oxide, germanium oxide, tantalum oxide, hafnium oxide, zirconium oxide, zinc oxide, barium oxide, gallium oxide and antimony oxide. The radiation-proof glass provided by the invention replaces the traditional lead oxide with lanthanum oxide, gadolinium oxide, hafnium oxide and tantalum oxide, so that the environment protection in the preparation process and the application period can be ensured, and the shielding rate of the glass is more than or equal to 95.1%; the radiation-proof glass obtained by adopting the components with specific dosage has better radiation-proof, glass forming and chemical stability, and the optical uniformity of the radiation-proof glass can reach 5 multiplied by 10 ‑6 Compared with the traditional PbO glass, the optical uniformity of the invention is improved by 1 order of magnitude, and the components provided by the invention are easy to prepare large-size high-uniformity radiation-proof glass.
Description
Technical Field
The invention belongs to the technical field of special glass preparation, and particularly relates to radiation-proof glass and a preparation method and application thereof.
Background
With the development of nuclear industry and medical health industry, the problem of protecting high-energy rays is more and more concerned. Among the many rays, gamma rays have been the focus of radiation protection research because of their extreme permeability and hazardousness. In principle, any material can be used for radiation protection, but the materials with better protection effect mainly comprise lead plates, concrete, inorganic glass, organic glass and the like, wherein the inorganic glass has good chemical stability, the components can be adjusted according to the protection requirement, and large-size transparent protective products are easy to prepare. At present, typical products of radiation-proof glass are ZF series glass, such as ZF3, ZF6, ZF7 and other brands. The ZF series glass has better gamma ray absorption capacity, but has serious lead pollution problem in the preparation process and application period due to high content of PbO, and lead glass waste generated in the preparation process is difficult to be treated harmlessly. Therefore, the existing radiation-proof glass causes serious environmental pollution.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that in the prior art, more waste materials are generated in the preparation of radiation-proof glass, harmless treatment is difficult, the radiation-proof property of the radiation-proof glass is difficult to ensure and the like, and provides the radiation-proof glass, and the preparation method and the application thereof.
Therefore, the invention provides the following technical scheme.
The invention provides radiation-proof glass, which comprises 15-25% of SiO in percentage by mass 2 、25-35％La 2 O 3 、10-20％Gd 2 O 3 、10％-20％GeO 2 、5％-15％Ta 2 O 5 、5％-10％HfO 2 、2％-8％ZrO 2 、2％-6％ZnO、1％-6％BaO、2％-6％Ga 2 O 3 、0.2％-1％Sb 2 O 3 。
Further, the components comprise 15-20% of SiO in percentage by mass 2 、30-35％La 2 O 3 、10-15％Gd 2 O 3 、10％-15％GeO 2 、5％-10％Ta 2 O 5 、5％-8％HfO 2 、2％-5％ZrO 2 、2％-4％ZnO、1％-3％BaO、2％-4％Ga 2 O 3 、0.2％-0.5％Sb 2 O 3 。
The invention also provides a preparation method of the radiation-proof glass, which comprises the following steps,
the radiation-proof glass is obtained by uniformly mixing the raw materials, melting at high temperature, forming and annealing.
The melting step comprises the step of melting the uniformly mixed raw materials for 4-6h at 1450-1550 ℃ to form molten glass.
The step of stirring the molten glass between the steps of melting and forming until a clarified homogenized molten glass is formed;
the rotation speed of the stirring is 50-80 rpm.
The stirring is carried out under an oxygen atmosphere;
introducing oxygen into the molten glass at a flow rate of 0.1-0.6L/min while stirring for 2-3 h; and introducing oxygen into the chamber in which the glass liquid is located at the flow rate of 1-5L/min for 4-6 h.
The stirring time of the glass liquid and the time of introducing oxygen into the chamber in which the glass liquid is positioned can be the same or different; the time for introducing oxygen into the chamber in which the molten glass is located is longer than the time for introducing oxygen into the molten glass.
And stirring the Pt crucible by adopting a Pt frame type stirrer to promote clarification and homogenization of the molten glass, wherein the stirring time is 1-6 h.
The forming step comprises the steps of cooling the glass liquid to 1150-1250 ℃, and then placing the glass liquid in a mold at 420-500 ℃ for forming.
The annealing temperature is 705-740 ℃, and the time is 4-6 h.
In addition, the invention also provides application of the radiation-proof glass or the radiation-proof glass prepared by the preparation method in medical treatment, nuclear power and nuclear test protection.
The radiation-proof glass is applied to gamma ray protection.
The technical scheme of the invention has the following advantages:
1. the radiation-proof glass provided by the invention comprises silicon oxide, lanthanum oxide, gadolinium oxide, germanium oxide, tantalum oxide, hafnium oxide, zirconium oxide, zinc oxide, barium oxide, gallium oxide and antimony oxide. The radiation-proof glass provided by the invention replaces the traditional lead oxide with lanthanum oxide, gadolinium oxide, hafnium oxide and tantalum oxide, so that the environment protection in the preparation process and the application period can be ensured, and the shielding rate of the glass is more than or equal to 95.1%; the radiation-proof glass obtained by adopting the components with specific dosage has good radiation-proof, glass-forming and chemical stability, and the optical uniformity of the radiation-proof glass can reach 5 multiplied by 10 -6 Compared with the traditional PbO glass, the optical uniformity of the invention is improved by 1 order of magnitude, and the components provided by the invention are easy to prepare large-size high-uniformity radiation-proof glass.
The radiation-proof glass provided by the embodiment of the invention has higher elastic modulus, transition temperature and chemical stability, and the application field of the radiation-proof glass is remarkably expanded.
2. The radiation-proof glass prepared by the method provided by the invention has good radiation-proof property, can ensure that the glass cannot form a Pt flash point by controlling the oxygen flow in the melting process, further cannot influence the optical uniformity and quality of the glass, can be used as optical glass, is environment-friendly in the preparation process, cannot generate substances influencing the environment, and has good protection capability and good chemical resistance stability.
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
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1450 ℃, melting at high temperature for 6 hours, after all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 30rpm for 6 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the molten glass is 0.1L/min, the ventilation time is 2 hours, the ventilation flow of the oxygen in the furnace chamber is 1L/min, the ventilation time is 6 hours, clarifying and homogenizing the molten glass, then cooling to 1150 ℃, placing the cooled molten glass into a preheated mold by adopting a leakage forming mode, when the mold is preheated to the temperature of 420 ℃, naturally forming a solid state, annealing the formed glass at the temperature of 720 ℃ for 4 hours, closing a power supply of an annealing furnace, naturally cooling to the room temperature, and obtaining the radiation-proof glass.
Example 2
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1450 ℃, melting at high temperature for 4 hours, stirring the batch by using a Pt stirrer at the rotating speed of 50rpm for 3 hours, simultaneously introducing oxygen into the glass liquid and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the glass liquid is 0.6L/min, the ventilation time is 3 hours, the ventilation flow of the oxygen in the furnace chamber is 5L/min, the ventilation time is 6 hours, the glass liquid forms clarified and homogenized glass liquid, cooling to 1150 ℃, placing the glass liquid into a preheated mold in a leakage forming mode, the preheating temperature of the mold is 460 ℃, naturally cooling to form a solid state, placing the formed glass at 735 ℃ for annealing for 6 hours, closing the power supply of an annealing furnace, naturally cooling to the room temperature, and obtaining the radiation-proof glass.
Example 3
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1550 ℃, melting at high temperature for 5 hours, stirring the batch by using a Pt stirrer at the rotation speed of 30rpm for 3 hours, simultaneously introducing oxygen into the glass liquid and a furnace chamber by using a Pt pipe, wherein the oxygen flow in the glass liquid is 0.1L/min, the air time is 3 hours, the oxygen flow in the furnace chamber is 2L/min, the air time is 4 hours, forming clarified and homogenized glass liquid, cooling to 1250 ℃, placing the cooled glass liquid into a preheating mould by adopting a material leakage forming mode, keeping the preheating temperature of the mould at 500 ℃, naturally forming a solid state, placing the formed glass at 730 ℃, annealing for 5 hours, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Example 4
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1500 ℃, melting at high temperature for 6 hours until all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 40rpm for 3 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the oxygen flow rate in the molten glass is 0.3L/min, the air time is 3 hours, the oxygen flow rate in the furnace chamber is 4L/min, the air time is 5 hours, forming clarified and homogenized molten glass, cooling to 1200 ℃, placing the cooled molten glass into a preheating mould in a leakage forming mode, wherein the preheating temperature of the mould is 480 ℃, naturally forming a solid state, placing the formed glass at 710 ℃, annealing for 4 hours, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Example 5
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1500 ℃, melting for 4 hours at high temperature, stirring the batch by using a Pt stirrer at the rotating speed of 40rpm for 3 hours, simultaneously introducing oxygen into the glass liquid and a furnace chamber by using a Pt pipe, wherein the flow rate of oxygen in the glass liquid is 0.5L/min, the ventilation time is 3 hours, the flow rate of oxygen in the furnace chamber is 5L/min, the ventilation time is 4 hours, forming clarified and homogenized glass liquid, cooling to 1250 ℃, placing the cooled glass liquid into a preheating mould by adopting a material leakage forming mode, the preheating temperature of the mould is 430 ℃, naturally forming a solid state, annealing the formed glass at 705 ℃ for 3 hours, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Example 6
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible at 1520 ℃, melting at high temperature for 4h, stirring the batch by using a Pt stirrer at the rotating speed of 50rpm for 3h, simultaneously introducing oxygen into the glass liquid and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the glass liquid is 0.1L/min, the ventilation time is 2h, the ventilation flow of the oxygen in the furnace chamber is 1L/min, the ventilation time is 6h to form clarified and homogenized glass liquid, cooling to 1150 ℃, placing the cooled glass liquid into a preheating mould in a material leakage forming mode, setting the preheating temperature of the mould to 460 ℃, naturally forming a solid state, annealing the formed glass at 740 ℃ for 6h, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Example 7
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible at 1520 ℃, melting at high temperature for 6h until all the ingredients form molten glass, stirring with a Pt stirrer at 30rpm for 4h, simultaneously introducing oxygen into the molten glass and the furnace chamber by adopting a Pt pipe, wherein the ventilation flow of the oxygen in the molten glass is 0.6L/min, the ventilation time is 3h, the ventilation flow of the oxygen in the furnace chamber is 5L/min, the ventilation time is 6h, the clarified and homogenized molten glass is formed, cooling to 1250 ℃, putting the cooled molten glass into a preheating mould by adopting a material leakage forming mode, and (3) preheating the mold at 430 ℃, annealing the formed glass at 720 ℃ for 4h after the glass naturally forms a solid state, turning off a power supply of the annealing furnace, and naturally cooling to room temperature to obtain the radiation-proof glass.
Example 8
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1550 ℃, melting at high temperature for 6 hours until all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 50rpm for 6 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the oxygen flow rate in the molten glass is 0.1L/min, the oxygen flow rate in the molten glass is 3 hours, the oxygen flow rate in the furnace chamber is 2L/min, and the oxygen time is 4 hours to form clarified and homogenized molten glass, cooling to 1150 ℃, placing the cooled molten glass into a preheating mould by adopting a material leakage forming mode, setting the preheating temperature of the mould to 420 ℃, annealing the formed glass at 720 ℃ for 5 hours after the formed glass naturally forms a solid state, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Example 9
The embodiment provides radiation-proof glass, and the components and the using amount refer to the table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1450 ℃, melting at high temperature for 6 hours until all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 30rpm for 6 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the molten glass is 0.1L/min, the ventilation time is 2 hours, the ventilation flow of the oxygen in the furnace chamber is 0.1L/min, the ventilation time is 6 hours, forming clarified and homogenized molten glass, cooling to 1150 ℃, placing the cooled molten glass into a preheating mould in a leakage forming mode, setting the preheating temperature of the mould to 420 ℃, naturally forming a solid state, annealing the formed glass at 720 ℃ for 4 hours, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Comparative example 1
The comparative example provides a radiation-resistant glass, the components and amounts of which are as shown in Table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1450 ℃, melting at high temperature for 6 hours, after all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 30rpm for 6 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the molten glass is 0.1L/min, the ventilation time is 2 hours, the ventilation flow of the oxygen in the furnace chamber is 1L/min, the ventilation time is 6 hours, clarifying and homogenizing the molten glass, then cooling to 1150 ℃, placing the cooled molten glass into a preheated mold by adopting a leakage forming mode, when the mold is preheated to the temperature of 420 ℃, naturally forming a solid state, annealing the formed glass at the temperature of 720 ℃ for 4 hours, closing a power supply of an annealing furnace, naturally cooling to the room temperature, and obtaining the radiation-proof glass.
Comparative example 2
The comparative example provides a radiation-resistant glass, the components and amounts of which are as shown in Table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1450 ℃, melting at high temperature for 6 hours, after all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 30rpm for 6 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the molten glass is 0.1L/min, the ventilation time is 2 hours, the ventilation flow of the oxygen in the furnace chamber is 1L/min, the ventilation time is 6 hours, clarifying and homogenizing the molten glass, then cooling to 1150 ℃, placing the cooled molten glass into a preheated mold in a leakage forming mode, when the mold is in a preheating temperature of 420 ℃, annealing the formed glass at 720 ℃ for 4 hours, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Comparative example 3
The comparative example provides a radiation-resistant glass, the components and amounts of which are as shown in Table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible at 1450 ℃, melting at high temperature for 6h, stirring the batch by using a Pt stirrer at the rotating speed of 30rpm for 6h after the batch completely forms molten glass, clarifying and homogenizing the molten glass, then cooling to 1150 ℃, placing the cooled molten glass into a preheated mold in a leakage forming mode at the preheating temperature of 420 ℃, annealing the formed glass at 720 ℃ for 4h after the molten glass forms a solid state, closing a power supply of an annealing furnace, and naturally cooling to room temperature to obtain the radiation-proof glass.
Comparative example 4
The comparative example provides a radiation-resistant glass, the components and amounts of which are as shown in Table 1;
the preparation method of the radiation-proof glass comprises the following steps,
weighing raw materials with corresponding mass according to the table 1, uniformly mixing to obtain a batch, adding the batch into a Pt crucible with the temperature of 1450 ℃, melting at high temperature for 6 hours, after all the batch forms molten glass, stirring the molten glass by using a Pt stirrer at the rotating speed of 30rpm for 6 hours, simultaneously introducing oxygen into the molten glass and a furnace chamber by using a Pt pipe, wherein the ventilation flow of the oxygen in the molten glass is 0.1L/min, the ventilation time is 2 hours, the ventilation flow of the oxygen in the furnace chamber is 1L/min, the ventilation time is 6 hours, clarifying and homogenizing the molten glass, then cooling to 1150 ℃, placing the cooled molten glass into a preheated mold in a leakage forming mode, when the mold is in a preheating temperature of 420 ℃, annealing the formed glass at 720 ℃ for 4 hours, closing a power supply of an annealing furnace, naturally cooling to room temperature, and obtaining the radiation-proof glass.
Test examples
The test example provides the performance test and test results of the radiation protection glasses obtained in examples 1 to 9 and comparative examples 1 to 4, and the components and the amounts of the respective examples and comparative examples are shown in table 1.
Table 1 components and amounts of radiation protective glasses of examples 1 to 9 and comparative examples 1 to 4
The test method of the radiation-proof glass is as follows, and the test results are shown in table 2.
The method for testing the shielding rate of the radiation-proof glass comprises the following steps: using a radiation source of 235 U, 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 detected Is provided with And A Light (es) And calculating the shielding rate (A) Light (es) -A Is provided with )/A Light (es) ×100％。
The method for testing the transmittance of the radiation-proof glass comprises the following steps: the test is carried out according to the method of GB/T2680-.
The method for testing the elastic modulus of the radiation-proof glass comprises the following steps: reference is made to GB/T7962.6-2010 section 6 of test method for colourless optical glass: young's modulus, shear modulus and Poisson's ratio.
The method for testing the transition temperature of the radiation-proof glass comprises the following steps: reference is made to GB/T7962.16-2010 section 16 of test method for colourless optical glass: linear expansion coefficient, transition temperature and sag temperature.
The method for testing the optical uniformity of the radiation-proof glass comprises the following steps: reference is made to GB/T7962.2-2010 section 2 of test method for colourless optical glass: the test is carried out by the method of optical uniformity-Fizeau planar interferometry.
The method for testing the water resistance stability of the radiation-proof glass comprises the following steps: the test was carried out according to the method of GB/T12416.2-1990 test method and grading of glass particles for Water resistance at 121 ℃.
The method for testing the acid resistance stability of the 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.
TABLE 2 results of performance test of radiation protective glasses obtained in examples and comparative examples
As can be seen from Table 2, the radiation-proof glass prepared by the invention has good transmittance, gamma ray resistance, elastic modulus, optical uniformity and chemical stability. The radiation-proof glass of comparative example 1, in which tantalum oxide and gadolinium oxide were removed and the amounts of the respective components were out of the range of the present invention, significantly reduced gamma ray protection ability of the glass, reduced transition temperature, and deteriorated chemical stability; the composition of the radiation protective glass of comparative example 2 is out of the range of the present invention, resulting in poor glass forming property and difficulty in forming homogeneous glass; the radiation-proof glass of comparative example 3 was prepared without oxygen, and Pt flash points were formed in the glass and could not be used as optical glass; in comparative example 4, when hafnium oxide and lanthanum oxide were removed, the shielding rate of the glass was significantly deteriorated.
The present invention providesRadiation-proof glass of, SiO 2 The anti-radiation glass is an important network forming body, the glass forming capability and the chemical stability of the glass can be improved, but the melting temperature of the glass can be increased due to excessive use amount of the anti-radiation glass, and the difficulty is brought to melting operation. The invention uses SiO 2 The mass content of the components is controlled to be 15-25%, preferably 15-20%, 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 15% by weight, glass formation and chemical properties are deteriorated; if the content of the component exceeds 25% by weight, the glass has a high melting temperature and an increased viscosity, and the radiation shielding ability is deteriorated.
La 2 O 3 The radiation-proof glass of the invention has the components necessary for radiation-proof capability, and can improve the capability of the glass for absorbing gamma rays. La 2 O 3 The mass content of the components is controlled to be 25-35 percent, and preferably 30-35 percent. If the mass content of the component is lower than 25 percent, the radiation protection capability of the glass is poor, and the application requirement of special environment is difficult to meet; if the content of the component exceeds 35% by weight, the glass forming property of the glass is deteriorated and it is difficult to form a homogeneous body.
Gd 2 O 3 The mass content of (A) is controlled to be 10-20%, preferably 10-15%. If the mass content of the component is less than 10 percent, the radiation resistance of the glass is poor, and the application requirement of special environment is difficult to meet; if the content of this component exceeds 15% by mass, the glass forming property of the glass is deteriorated and it is difficult to form a homogeneous body.
GeO 2 Is an important network former of radiation-proof glass, can improve the glass forming capability and chemical stability of the glass, and the mass content of the component is controlled to be 10-20%, preferably 10-15%. If the mass content of the component is less than 10%, the glass has poor glass-forming property; if the content of this component exceeds 20% by mass, the elastic modulus and chemical stability of the glass are deteriorated.
Ta 2 O 5 The radiation-proof glass is a necessary component with good elastic modulus and chemical stability, the mass content of the component is controlled to be 5-15%, preferably 5-10%, and the densification of the glass structure can be promotedAnd (3) the acid resistance stability of the glass is improved. If the weight percentage of the component is less than 5 percent, the improvement on the elastic modulus and the chemical stability of the glass is not obvious; if the content of the component exceeds 15% by weight, Ta 2 O 5 It is difficult to sufficiently melt the glass, and the glass-forming property is deteriorated.
HfO 2 Is a component necessary for radiation-proof glass to have higher transition temperature and chemical stability, and the weight percentage of the component is controlled to be 5-10 percent, and the preferred weight percentage is 5-8 percent. If the weight percentage of the component is less than 5 percent, the glass transition temperature and the chemical stability are not obviously improved; if the content of this component exceeds 10% by weight, HfO 2 It is difficult to sufficiently melt the glass, and the glass-forming property is deteriorated.
ZrO 2 Action in radiation-proof glass and HfO 2 Similarly, if the weight percentage of the component is less than 2 percent, the radiation resistance of the glass is poor, and the requirements of special environment application are difficult to meet; if the content of the component exceeds 8% by weight, the glass forming property of the glass is deteriorated and it is difficult to form a homogeneous body.
ZnO is a component necessary for the radiation-proof glass to have excellent chemical stability, and the weight percentage of the component is controlled to be 2-6%, and preferably 2-5%. If the mass content of the component is less than 2 percent, the chemical stability of the glass is not obviously improved; if the content of the component exceeds 5% by weight, ZnO will cause phase separation in the glass, lowering the glass transmittance.
BaO can improve the gamma ray absorption capacity of the glass, and if the mass content of the component is lower than 1%, the protection capacity of the glass is not obviously improved; if the heavy weight content of this component exceeds 6%, the glass elastic modulus and the transition temperature decrease.
Ga 2 O 3 Belongs to a glass network intermediate and is used for improving the glass forming property of glass. If the mass content of the component is lower than 2 percent, the glass forming property of the glass is not obviously improved; if the content of this component exceeds 6% by mass, the glass is degraded in chemical stability.
Sb 2 O 3 The components are used as a defoaming agent of radiation-proof glass. If the component isThe mass content is less than 0.2%, bubbles in the glass can not be completely eliminated, and homogeneous glass can not be obtained; if the content of this component exceeds 1% by mass, the excessive fining agent does not react completely, 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 radiation-proof glass is characterized by comprising 15-25 mass percent of SiO 2 、25-35%La 2 O 3 、10-20%Gd 2 O 3 、10%-20%GeO 2 、5%-15%Ta 2 O 5 、5%-10%HfO 2 、2%-8%ZrO 2 、2%-6%ZnO、1%-6%BaO、2%-6%Ga 2 O 3 、0.2%-1%Sb 2 O 3 And (4) forming.
2. The radiation-protective glass according to claim 1, wherein the composition thereof comprises, in mass percent, 15-20% SiO 2 、30-35%La 2 O 3 、10-15%Gd 2 O 3 、10%-15%GeO 2 、5%-10%Ta 2 O 5 、5%-8%HfO 2 、2%-5%ZrO 2 、2%-4%ZnO、1%-3%BaO、2%-4%Ga 2 O 3 、0.2%-0.5%Sb 2 O 3 And (4) forming.
3. The method for producing a radiation protective glass according to claim 1 or 2, comprising the steps of,
the radiation-proof glass is obtained by uniformly mixing the raw materials, melting at high temperature, forming and annealing.
4. The method as claimed in claim 3, wherein the melting step comprises melting the uniformly mixed raw materials at 1450-1550 ℃ for 4-6h to form the molten glass.
5. A method of making as claimed in claim 3 or claim 4 further comprising the step of stirring the molten glass between said steps of melting and forming until a clarified homogenized molten glass is formed;
the rotation speed of the stirring is 50-80 rpm.
6. The production method according to claim 5, wherein the stirring is performed under an oxygen atmosphere;
introducing oxygen into the molten glass at a flow rate of 0.1-0.6L/min while stirring for 2-3 h; and introducing oxygen into the chamber in which the glass liquid is located at the flow rate of 1-5L/min for 4-6 h.
7. The method as claimed in claim 3, 4 or 6, wherein the step of forming comprises cooling the molten glass to 1250 ℃ of 1150-.
8. The method as claimed in claim 3, 4 or 6, wherein the annealing temperature is 705-740 ℃ and the annealing time is 4-6 h.
9. Use of the radiation protective glass according to any one of claims 1 to 2 or the radiation protective glass produced by the production method according to any one of claims 3 to 8 in medical treatment, nuclear power and nuclear test protection.
10. Use according to claim 9, wherein the radiation protective glass is used for gamma radiation protection.
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