Irradiation-resistant glass having γ-ray shielding and neutron protection functions and preparation method therefor

Abstract

Irradiation-resistant glass having γ-ray shielding and neutron protection functions and a preparation method therefor. The glass material is prepared from the following components in percentage by mass: 25-45% of SiO2, 45-55% of PbO, 0.5-5% of Gd2O3, 0.5-1.5% of CeO2, 0.5-5% of Al2O3, 0-10% of Na2O, 2-10% of K2O, and 0-3% of an alkaline earth metal oxide selected from at least one of CaO and MgO, CaO and MgO being not both 0. The glass material has excellent gamma ray shielding performance, a good neutron protection function, and irradiation resistance, can be used for preparing a nuclear radiation shielding window, and has wide popularization and application prospects in complex environments in which gamma rays and neutron radiation are both present, e.g., nuclear power stations, nuclear power facilities, radiation diagnosis and treatment, and space detection.

Description

Radiation-resistant glass with gamma-ray shielding and neutron protection functions and preparation method thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to Chinese application CN202311660224.0, filed on December 6, 2023, entitled “Radiation-resistant glass with gamma-ray shielding and neutron protection functions and preparation method thereof.” The entire contents of the above application are incorporated herein by reference for all purposes. Technical Field

[0003] The present application relates to the field of glass technology, and in particular to a radiation-resistant glass with gamma-ray shielding and neutron protection functions and a preparation method thereof. Background Art

[0004] Any discussion of the prior art throughout the specification should not be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.

[0005] Effective radiation protection is crucial in the application of nuclear energy and radioactive materials, particularly in nuclear power plants, nuclear power facilities, radiological diagnosis and treatment, and space exploration. Nuclear reactions release high-energy radiation or particles such as alpha, beta, and gamma rays and neutrons, posing a serious threat to human health and the proper functioning of equipment. Nuclear radiation shielding windows, crucial for researchers and operators observing nuclear waste solidification, spent fuel purification, and nuclear material processing from the side of the operating room, require extremely high shielding and radiation resistance.

[0006] In radiation protection, alpha and beta rays are usually not the main focus due to their weak penetrating power and easy absorption. In contrast, the high energy and strong penetrating power of gamma rays and neutrons make them the focus of consideration for shielding materials. Existing gamma ray shielding methods mainly rely on high-density materials such as lead or lead-based alloys, which can effectively absorb gamma rays due to their high atomic number. However, these materials are usually heavy, have poor flexibility, and their performance degrades under long-term radiation exposure. For neutron shielding, materials containing a large amount of light elements (such as hydrogen) are usually required because light elements can effectively slow down and absorb neutrons. Commonly used neutron shielding materials include boron-containing polyethylene and water. However, these materials generally perform poorly in gamma ray shielding and do not have the required mechanical strength and chemical stability, which limits their scope of application.

[0007] Currently, few shielding materials on the market can effectively shield gamma rays and neutrons at the same time. They also have problems such as heavy weight, no optical transmittance or low optical transmittance, and reduced performance under long-term radiation. Summary of the Invention

[0008] The present invention provides radiation-resistant glass with gamma-ray shielding and neutron protection functions and a preparation method. The glass material provided by the present invention has excellent gamma-ray shielding properties, good neutron protection, and radiation resistance. It can be used to make nuclear radiation shielding windows and has broad application prospects in complex environments such as nuclear power plants, nuclear power facilities, radiological diagnosis and treatment, and space exploration, where gamma-ray and neutron radiation coexist.

[0009] Specifically, the present invention provides the following technical solutions.

[0010] In a first aspect of the present invention, a glass material is provided, comprising or consisting of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 0.5%-5% Gd2O3, 0.5%-1.5% CeO2, 0.5%-5% Al2O3, 0%-10% Na2O, 2%-10% K2O, and 0-3% of at least one alkaline earth metal oxide selected from CaO and MgO, wherein the CaO and MgO are not both zero.

[0011] In some embodiments of the present invention, the glass material contains the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 0.5%-5% Gd2O3, 0.5%-1.5% CeO2, 0.5%-5% Al2O3, 0%-10% Na2O, 2%-10% K2O, and 0.1%-3% of an alkaline earth metal oxide selected from at least one of CaO and MgO.

[0012] In some embodiments of the present invention, the glass material is composed of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 0.5%-5% Gd2O3, 0.5%-1.5% CeO2, 0.5%-5% Al2O3, 0%-10% Na2O, 2%-10% K2O, and 0.1%-3% of at least one alkaline earth metal oxide selected from CaO and MgO, and the sum of the contents of all components is 100%.

[0013] According to an embodiment of the present invention, when the glass material of the present invention is 20 mm thick, 60 The shielding rate of Co gamma rays is ≥40.47%; the shielding rate for thermal neutrons is ≥92.63%; the transmittance at 560nm is ≥86.42%, and the transmittance at 560nm after irradiation with a total dose of 10,000 Gy of gamma rays is ≥82.61%. The transmittance at 560nm decreases by ≤6.67% after irradiation with a total dose of 10,000 Gy of gamma rays.

[0014] SiO2, as a glass-forming oxide, is the primary component forming the glass skeleton network structure. In the above-described embodiment of the present invention, the mass percentage of SiO2 is 25%-45%. Further, the mass percentage of SiO2 can be 25%-40%, 40%-45%, 25%-30%, 25%-29%, 25%-28%, 25%-27%, 28%-40%, 30%-40%, 30%-31%, 31%-40%, 25%-31%, 28%-31%, and so on. In the glass composition of the present invention, the above-described SiO2 content helps provide structural stability and chemical durability, and helps maintain transparency and radiation resistance. Excessively high SiO2 content can increase the melting point of the glass, making the glass melting and processing difficult and increasing costs. Excessively low SiO2 content can lead to an instability of the glass skeleton network structure, thereby reducing the structural stability and chemical durability of the glass, potentially making the glass more susceptible to chemical corrosion and environmental factors, and affecting the optical properties of the glass.

[0015] Lead is a heavy metal element with a high atomic number and a high mass attenuation coefficient. Therefore, PbO is widely used in radiation shielding. As the PbO content increases, the shielding material often exhibits better radiation shielding capabilities. However, excessive PbO content can reduce the thermal stability of the glass, affect its visible light transmittance, and cause it to yellow. It also poses environmental and health risks. In the above-mentioned embodiment of the present invention, the PbO content is 45%-55% by weight. In the glass composition of the present invention, this PbO content helps balance the glass's radiation shielding ability, optical transmittance, and radiation resistance. And, further, in the above-mentioned embodiment of the present invention, the mass percentage of PbO can be 46%-55%, 48%-55%, 48.7%-55%, 50%-55%, 51%-55%, 52%-55%, 53%-55%, 54%-55%, 45%-53%, 48%-53%, 48.7%-53%, 50%-53%, 45%-50%, 46%-50%, 48%-50%, 48.7%-50%, 45%-48.7%, 46%-48.7%, 48%-48.7%, 45%-48%, 46%-48% and so on.

[0016] Gd has a large thermal neutron absorption cross section ( 155 Gd thermal neutron microscopic absorption cross section 61000 barns and 157Gd (Gd) has a thermal neutron microscopic absorption cross section of 255,000 barns and is widely used in nuclear physics and nuclear medicine for neutron shielding and neutron capture. However, the inventors have discovered that the addition of Gd2O3 often affects the transparency and chemical stability of the glass. In particular, when excessive Gd is added, the glass is prone to phase separation, which affects spectral transmittance. In the above-mentioned embodiment of the present invention, the mass percentage of Gd2O3 is 0.5%-5%, and can further be 1%-5%, 2%-5%, 3%-5%, 4%-5%, 1%-3%, 2%-3%, 3%-4%, 0.5%-3%, and so on. In the glass composition of the present invention, the above-mentioned Gd2O3 content helps balance the radiation shielding ability, chemical stability, and optical transmittance of the glass material.

[0017] CeO2 is usually used as a stabilizer and exists in the glass structure. Electricity price balance, where Ce 3+ It has a tendency to capture holes and be oxidized to form Ce 3+(+) , Ce 4+ It has a tendency to capture free electrons and be reduced to form Ce 4+(-) , preventing the free electrons generated by irradiation from entering defects in the glass structure, thereby preventing the formation of color centers and avoiding glass coloration. However, excessive CeO2 may cause the glass to change color, affecting its transparency and aesthetics. In the above-mentioned embodiments of the present invention, excessively high or low CeO2 content will affect the optical properties of the glass material and reduce optical transmittance. Excessive CeO2 content will also affect the viscosity and fluidity of the glass melt, affecting the melting process, and affecting the structural integrity and mechanical properties of the glass. Excessively low CeO2 content will reduce the chemical stability of the glass material and reduce the glass material's ability to block ultraviolet rays and radiation. In the above embodiment of the present invention, the mass percentage of CeO2 is 0.5%-1.5%, and can further be 0.5%-1.2%, 0.5%-1%, 0.5%-0.6%, 1%-1.5%, 1%-1.2%, 0.6%-1.5%, 0.6%-1.2%, 0.6%-1% and so on. In the glass composition of the present invention, the above content of CeO2 helps to balance the optical properties, chemical stability, structural stability, etc. of the glass material.

[0018] Na2O and K2O are network oxides in glass. Alkali metal ions easily migrate and diffuse within the glass, reducing the viscosity of the glass during high-temperature melting, making it easier to melt, and thus serving as a good flux. In the present invention, the inventors discovered that excessive Na2O and K2O content can reduce the chemical stability, thermal stability, and mechanical strength of the glass, increase its thermal expansion coefficient, and easily induce greater stress in the glass under temperature fluctuations, affecting its optical properties such as transmittance and optical uniformity. Furthermore, it can dilute the concentration of high-atomic-number elements in the glass, reducing radiation shielding effectiveness and leading to reduced stability. In order to better balance the above properties and obtain a glass material with better comprehensive performance, in the above embodiment of the present invention, the mass percentage of K2O is 2%-10%, and can further be 2%-6.9%, 2%-6.8%, 2%-3.9%, 2%-2.5%, 2.5%-10%, 2.5%-6.9, 2.5%-6.8%, 2.5%-3.9%, 3.9%-10%, 3.9%-6.9, 3.9%-6.8, 6.8%-10%, 6.8%-6.9, 6.9%-10%, and so on. The mass percentage of Na2O is 0%-10%, and can further be 0%-2%, 0-4%, 0-4.5%, 0-7.3%, 2%-7.3%, 2%-4.5%, 2%-4%, 4%-10%, 4%-7.3%, 4%-4.5%, 4.5%-10%, 4.5%-7.3% and so on.

[0019] Al2O3 is a network intermediate that forms the glass structure. Its content affects the thermal expansion coefficient and chemical and thermal stability of the glass. Al2O3 can increase the machinability of the glass, but too much can reduce the material properties. During the research process, the inventors found that even a small amount of Al2O3 can cause tiny crystals in the glass because the solubility of Al2O3 in the glass melt is very poor. If the glass melt contains Al2O3, even a small amount of Al2O3 must increase the melting temperature to about 1550°C to obtain a transparent glass melt. However, such a high melting temperature is undesirable and uneconomical.

[0020] CaO and MgO are alkaline earth metal oxides that form network-external oxides within the glass structure. During research, the inventors discovered that the addition of CaO and / or MgO affects the optical transmittance and chemical stability of the glass. Excessive addition also dilutes the concentration of lead or gadolinium, compromising radiation shielding effectiveness.

[0021] In the above-mentioned embodiment of the present invention, the inventors discovered that by simultaneously adding a specific amount of Al2O3 and at least one alkaline earth metal oxide selected from CaO and MgO to a glass material composition containing 25%-45% SiO2, 45%-55% PbO, 0.5%-5% Gd2O3, 0.5%-1.5% CeO2, 0%-10% Na2O and 2%-10% K2O, the prepared glass material not only has good optical transmittance but also has good radiation shielding capability. In particular, the glass material of the present invention has a maximum high-temperature melting temperature of only 1350°C during preparation. The specific amount of Al2O3 described in the present invention is 0.5%-5% by weight, and this content can further be 0.5%-4%, 0.5%-3%, 0.5%-2%, 0.5%-1%, 1%-5%, 1%-3%, 1%-2%, 2%-5%, 2%-3%, 3%-5%, etc. The specific amount of alkaline earth metal oxide selected from at least one of CaO and MgO described in the present invention, wherein the mass percentage of the alkaline earth metal oxide selected from at least one of CaO and MgO is 0.1%-3%, preferably 0.5%-2.5%, and can further be selected from 0.5%-2%, 1.5%-2.5%, and particularly 1.5%-2%. In particular, in some embodiments of the present invention, the mass percentage of CaO is 0-2%, preferably 0.5%-2%, and more preferably 1%-2%. The mass percentage of MgO is 0-1%, preferably 0-0.5%, more preferably 0.5%-1%, more preferably 0.5% or 0.

[0022] In particular, in some embodiments of the present invention, the glass material is composed of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 2%-7.3% or 0% Na2O, 2%-10% K2O, and 0.1%-3% of an oxide selected from at least one of CaO and MgO, and the sum of the contents of all components is 100%.

[0023] In particular, in some embodiments of the present invention, the glass material is composed of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 2%-7.3% or 0% Na2O, 2%-10% K2O, 0.5%-2% CaO and 0-1% MgO, and the sum of the contents of all components is 100%.

[0024] In particular, in some embodiments of the present invention, the glass material is composed of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 2%-7.3% or 0% Na2O, 2%-10% K2O, 1.5%-2% CaO and 0-1% MgO, and the sum of the contents of all components is 100%.

[0025] In particular, in some embodiments of the present invention, the glass material is composed of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 2%-7.3% or 0% Na2O, 2%-10% K2O, 0.5%-2% CaO, and the sum of the contents of all components is 100%.

[0026] In particular, in some embodiments of the present invention, the glass material is composed of the following components in percentage by mass: 25%-45% SiO2, 45%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 2%-7.3% or 0% Na2O, 2%-10% K2O, 1%-1.5% CaO and 0.5-1% MgO, and the sum of the contents of all components is 100%.

[0027] The various specific technical features described in the above embodiments of the present invention can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further explain various possible combinations.

[0028] Unless otherwise specified, the numerical ranges described in the present invention include all values ​​within this range, and include ranges consisting of any two values ​​within this range. For example, 1.5%-2% includes all values ​​between 1.5% and 2%, and includes ranges consisting of any two values ​​within this range (for example, 1.51% and 1.99%) (1.51%-2%, 1.99%-2%, and 1.51%-1.99%). Different numerical values ​​of the same indicator appearing in all embodiments of the present invention can be arbitrarily combined to form a range value.

[0029] In a second aspect of the present invention, a method for preparing the glass material described in the first aspect is provided, which comprises: mixing raw materials, melting at high temperature, clarifying with auxiliary stirring, cooling and forming, and precision annealing.

[0030] In an embodiment of the present invention, the high temperature melting temperature is 1235-1350°C, the forming temperature is 1108-1222°C, and the annealing temperature is 405-450°C.

[0031] In a third aspect of the present invention, a radiation shielding material is provided, which comprises the glass material described in the first aspect or is made of the glass material described in the first aspect.

[0032] In an embodiment of the present invention, the radiation shielding material is used to shield gamma rays and / or neutron radiation.

[0033] In a fourth aspect of the present invention, an optical element is provided, which comprises the glass material described in the first aspect or is made of the glass material described in the first aspect.

[0034] In one embodiment of the invention, the optical element is a radiation shielding optical window element; the radiation is in particular gamma ray radiation and / or neutron radiation.

[0035] In a fifth aspect of the present invention, there is provided an application of the glass material described in the first aspect, the radiation shielding material described in the third aspect, or the optical element described in the fourth aspect in the field of radiation shielding or the field of optics.

[0036] In some embodiments of the present invention, the applications include, but are not limited to, use in the fields of nuclear power plant facilities, nuclear power facilities, radiation diagnosis and treatment, and space exploration.

[0037] By using one or more of the above technical means, the following beneficial effects can be achieved:

[0038] The present invention provides a radiation-resistant glass with gamma ray shielding and neutron protection functions, the glass material has excellent gamma ray shielding performance, good neutron protection function and radiation resistance, and has good optical transmittance, wherein the glass material has a thickness of 20 mm and has a good optical transmittance. 60 The Co gamma-ray shielding efficiency is greater than 40.47%, the thermal neutron shielding efficiency is greater than 92.63%, and the transmittance at 560 nm is greater than 86.42%. Even after irradiation with a total gamma-ray dose of 10,000 Gy, the transmittance at 560 nm remains above 82.61%, with a decrease of ≤6.67% after irradiation with a total gamma-ray dose of 10,000 Gy. This glass material can be used to manufacture nuclear radiation shielding windows and has broad application prospects in complex environments where gamma-ray and neutron radiation coexist, such as nuclear power plants, nuclear power facilities, radiological diagnosis and treatment, and space exploration. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The drawings constituting part of the present application are provided to provide a further understanding of the present application. The illustrative embodiments and their descriptions of the present application are provided to explain the present application and do not constitute an undue limitation on the present application. The following describes the implementation scheme of the present application in detail in conjunction with the drawings, wherein:

[0040] Figure 1 252 Neutron energy spectrum obtained by moderating Cf source neutrons through polyethylene.

[0041] FIG2 shows a comparison of the transmittance (at 560 nm) of the glass material of Example 6 of the present invention before and after irradiation with a total dose of 10,000 Gy of gamma rays. DETAILED DESCRIPTION

[0042] The present application will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present application only and are not intended to limit the scope of the present application. The experimental methods in the following examples where specific conditions are not specified are generally performed under conventional conditions or as recommended by the manufacturer.

[0043] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. The reagents or raw materials used in this application can be purchased through conventional channels. Unless otherwise specified, the reagents or raw materials used in this application are used in a conventional manner in this area or in accordance with the product instructions. In addition, any methods and materials similar to or equivalent to those described herein can be applied to the present method. The preferred embodiments and materials described herein are for demonstration purposes only.

[0044] The performance parameters in the following examples were measured using the following methods:

[0045] Conducted by China Academy of Engineering Physics 60 Co gamma ray shielding test. The sample size is 150×150×50mm. A NaI detector is used to measure the radiation background in the experimental space. The counts n of the two gamma ray full energy peaks of 1.173MeV and 1.332MeV after the radiation passes through the shielding material, as well as the count n0 when there is no sample. The software is used to analyze and process the data, remove the background, and obtain 60 The net count of the two γ-ray full energy peaks of Co is taken as the full energy peak count. Calculate the gamma-ray shielding efficiency I of the material.

[0046] The transmittance was tested using a UV-visible-infrared spectrophotometer.

[0047] Thermal neutron shielding efficiency test: use 252 The Cf source produces neutrons and uses polyethylene as a moderator to slow down the fast neutrons into thermal neutrons. 252The neutron spectrum obtained by slowing down the Cf source neutrons through polyethylene is shown in Figure 1. 3 The He proportional counter detects the response count rate of thermal neutrons and fast neutrons. This count rate includes the total response of thermal neutrons and fast neutrons that are not shielded by materials. In order to obtain the response count rate of fast neutrons alone, a layer of cadmium is wrapped around the detector. Since cadmium has a strong absorption effect on thermal neutrons, this can shield the response of thermal neutrons and only measure the response count rate of fast neutrons. The response count rate of "thermal neutrons + fast neutrons" when no sample is added during the test is recorded as N'0, and the response count rate of "fast neutrons" only is recorded as N' 0b The “thermal neutron + fast neutron” response count rate after adding the sample to be tested is recorded as N′ s , only the “fast neutron” response count rate is recorded as N′ sb The thermal neutron shielding rate of the material k th It can be calculated using the following formula, which reflects the change in the thermal neutron response count rate before and after the addition of the sample to be tested, thereby measuring the shielding effect of the material on thermal neutrons:

[0048] Example 1

[0049] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 40% SiO2, 46% PbO, 5% Gd2O3, 0.5% CeO2, 0.5% Al2O3, 4.5% Na2O, 2% K2O, 1% CaO, and 0.5% MgO.

[0050] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is made from quartz sand, aluminum oxide, calcium carbonate, magnesium carbonate, red lead, cerium oxide, sodium carbonate, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1301°C, clarified with auxiliary stirring, mechanically formed at 1158°C, and annealed at 438°C to obtain the obtained material.

[0051] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 40.78%, the thermal neutron shielding rate of the 20 mm thick sample is 96.00%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 83.55% (a decrease of 6.46%).

[0052] Example 2

[0053] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 30% SiO2, 53% PbO, 4% Gd2O3, 0.6% CeO2, 1% Al2O3, 4% Na2O, 6.9% K2O, and 0.5% CaO.

[0054] The radiation-resistant glass material for gamma ray shielding and neutron protection in this embodiment is prepared from quartz sand, aluminum oxide, calcium carbonate, lead silicate, cerium oxide, sodium nitrate, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1257°C, clarified with auxiliary stirring, mechanically formed at 1130°C, and annealed at 411°C to obtain the obtained material.

[0055] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 43.23%, the thermal neutron shielding rate of the 20 mm thick sample is 95.36%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 83.00% (a decrease of 4.02%).

[0056] Example 3

[0057] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 45% SiO2, 45% PbO, 2% Gd2O3, 0.5% CeO2, 1% Al2O3, 2% Na2O, 2.5% K2O, 1% CaO, and 1% MgO.

[0058] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is made from quartz sand, aluminum hydroxide, calcium carbonate, magnesium carbonate, yellow lead, cerium oxide, sodium carbonate, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1350°C, clarified with auxiliary stirring, mechanically formed at 1222°C, and annealed at 450°C to obtain the obtained material.

[0059] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 40.47%, the thermal neutron shielding rate of the 20mm thick sample is 93.65%, and the transmittance (at 560nm) of the 20mm thick sample after irradiation with a total dose of 10000Gy of gamma rays is 82.95 (a decrease of 6.67%).

[0060] Example 4

[0061] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 31% SiO2, 48% PbO, 0.5% Gd2O3, 1.5% CeO2, 5% Al2O3, 10% Na2O, 3.9% K2O, and 0.1% MgO.

[0062] The radiation-resistant glass material for gamma ray shielding and neutron protection in this embodiment is prepared from quartz sand, aluminum hydroxide, magnesium carbonate, lead silicate, cerium oxide, sodium nitrate, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1266°C, clarified with auxiliary stirring, mechanically formed at 1138°C, and annealed at 415°C to obtain the obtained material.

[0063] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 42.10%, the thermal neutron shielding rate of the 20 mm thick sample is 92.63%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 82.61% (a decrease of 3.81%).

[0064] Example 5

[0065] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 28% SiO2, 48.7% PbO, 1% Gd2O3, 1% CeO2, 2% Al2O3, 7.3% Na2O, 10% K2O, 1.5% CaO, and 0.5% MgO.

[0066] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is made from quartz sand, aluminum hydroxide, calcium carbonate, magnesium carbonate, red lead, cerium oxide, sodium carbonate, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1235°C, clarified with auxiliary stirring, mechanically formed at 1108°C, and annealed at 405°C to obtain the obtained material.

[0067] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 42.49%, the thermal neutron shielding rate of the 20 mm thick sample is 93.13%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 84.26% (a decrease of 4.42%).

[0068] Example 6

[0069] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 25% SiO2, 55% PbO, 3% Gd2O3, 1.2% CeO2, 3% Al2O3, 4% Na2O, 6.8% K2O, and 2% CaO.

[0070] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is made from quartz sand, aluminum hydroxide, calcium carbonate, red lead, cerium oxide, sodium carbonate, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1241°C, clarified with auxiliary stirring, mechanically formed at 1117°C, and annealed at 408°C to obtain the obtained material.

[0071] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 43.36%, the thermal neutron shielding rate of the 20 mm thick sample is 94.97%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 84.40% (a decrease of 5.33%).

[0072] Example 7

[0073] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is composed of the following components in percentage by mass: 35% SiO2, 50% PbO, 2% Gd2O3, 1.5% CeO2, 3% Al2O3, 6% K2O, 2% CaO, and 0.5% MgO.

[0074] The radiation-resistant glass material with gamma ray shielding and neutron protection functions of this embodiment is made from quartz sand, aluminum oxide, calcium carbonate, magnesium carbonate, red lead, cerium oxide, potassium carbonate, and gadolinium oxide. The raw materials are mixed in proportion, melted at 1245°C, clarified with auxiliary stirring, mechanically formed at 1110°C, and annealed at 420°C to obtain the obtained material.

[0075] The 20 mm thick sample of the radiation-resistant glass material with gamma ray shielding and neutron protection functions prepared by the method of this embodiment 60 The Co gamma ray shielding rate is 43.08%, the thermal neutron shielding rate of the 20 mm thick sample is 93.97%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 82.89% (a decrease of 4.22%).

[0076] Comparative Example 1

[0077] The glass material of this comparative example consists of the following components in percentage by mass: 48% SiO2, 37.5% PbO, 1.5% CeO2, 10% Na2O, and 3% K2O.

[0078] The glass material of this comparative example was prepared using quartz sand, red lead, cerium oxide, sodium carbonate and potassium carbonate as raw materials according to the method of Example 1.

[0079] The 20 mm thick sample of the glass material in this comparative example 60 The Co gamma ray shielding rate is 20.48%, the thermal neutron shielding rate of the 20 mm thick sample is 80.46%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 70.19% (a decrease of 10.96%).

[0080] Comparative Example 2

[0081] The glass material of this comparative example is composed of the following components in percentage by mass: 48.6% SiO2, 24.2% PbO, 7.5% Gd2O3, 18.1% K2O, 1.4% CeO2, and 0.2% F. The glass material of this comparative example is prepared using quartz sand, red lead, gadolinium oxide, cerium oxide, potassium carbonate, and potassium fluorosilicate as raw materials, according to the method of Example 1.

[0082] The 20 mm thick sample of the glass material in this comparative example 60 The Co gamma ray shielding rate is 19.02%, the thermal neutron shielding rate of the 20 mm thick sample is 96.26%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 58.35% (a decrease of 6.76%).

[0083] Comparative Example 3

[0084] The glass material of this comparative example consists of the following components in percentage by mass: 26.49% SiO2, 66.23% PbO, 5.68% Gd2O3, and 1.60% K2O.

[0085] The glass material of this comparative example was prepared using quartz sand, red lead, potassium nitrate and gadolinium oxide as raw materials according to the method of Example 1.

[0086] The 20 mm thick sample of the glass material in this comparative example 60 The Co gamma ray shielding rate is 44.63%, the thermal neutron shielding rate of the 20 mm thick sample is 95.90%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 48.28% (a decrease of 35.72%).

[0087] Comparative Example 4

[0088] The glass material of this comparative example consists of the following components in percentage by mass: 28% SiO2, 55% PbO, 3% Gd2O3, 1.2% CeO2, 4% Na2O, 6.8% K2O, and 2% CaO.

[0089] The glass material of this comparative example was prepared using quartz sand, red lead, cerium oxide, sodium carbonate, potassium nitrate, gadolinium oxide and calcium carbonate as raw materials according to the method of Example 1.

[0090] The 20 mm thick sample of the glass material in this comparative example 60 The Co gamma ray shielding rate is 39.99%, the thermal neutron shielding rate of the 20 mm thick sample is 92.42%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 52.61% (a decrease of 16.60%).

[0091] Comparative Example 5

[0092] The glass material of this comparative example consists of the following components in percentage by mass: 27% SiO2, 55% PbO, 3% Gd2O3, 1.2% CeO2, 3.0% Al2O3, 4% Na2O, and 6.8% K2O.

[0093] The glass material of this comparative example was prepared according to the method of Example 1 using quartz sand, red lead, gadolinium oxide, cerium oxide, sodium carbonate, potassium nitrate and gadolinium oxide as raw materials.

[0094] The 20 mm thick sample of the glass material in this comparative example 60 The Co gamma ray shielding rate is 40.86%, the thermal neutron shielding rate of the 20 mm thick sample is 92.99%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 49.38% (a decrease of 21.84%).

[0095] Comparative Example 6

[0096] The glass material of this comparative example is composed of the following components in percentage by mass: 53.8% SiO2, 24.2% PbO, 2.4% (Li-6)2O, 1.2% Na2O, 14.6% K2O, 1.8% CeO2, and 2% B2O3. This comparative example glass material was prepared using quartz sand, red lead, cerium oxide, sodium carbonate, potassium carbonate, boric acid, and lithium oxide as raw materials according to the method of Example 1.

[0097] The 20 mm thick sample of the glass material in this comparative example 60The Co gamma ray shielding rate is 23.26%, the thermal neutron shielding rate of the 20 mm thick sample is 92.77%, and the transmittance (at 560 nm) of the 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays is 55.23% (a decrease of 11.12%).

[0098] The compositions and properties of the glass samples of Examples 1 to 7 and Comparative Examples 1 to 6 of the present invention are shown in Table 1 and Table 2, respectively. Table 1 Composition of the glass samples of Examples 1 to 7 and Comparative Examples 1 to 6

[0099] Table 2 Performance test results of glass samples of Examples 1 to 7 and Comparative Examples 1 to 6

[0100] As shown in Table 2, the radiation-resistant glass materials with gamma ray shielding and neutron protection functions of each embodiment are as follows: 60 The Co gamma ray shielding rate is ≥40.47%; in some embodiments of the present invention, the thermal neutron shielding rate of a 20 mm thick sample is ≥92.63%; in some embodiments of the present invention, the transmittance (at 560 nm) of a 20 mm thick sample after irradiation with a total dose of 10,000 Gy of gamma rays decreases by ≤6.67%.

[0101] The various specific technical features described in the above embodiments of the present invention can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further explain various possible combinations.

[0102] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art may still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein with equivalents. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A glass material, which consists of the following components in percentage by mass: 25%-45% SiO2, 48%-55% PbO, 0.5%-5% Gd2O3, 0.5%-1.5% CeO2, 0.5%-5% Al2O3, 4%-10% Na2O, 6.8%-10% K2O, and 0-3% of an alkaline earth metal oxide selected from at least one of CaO and MgO, and CaO and MgO are not 0 at the same time.

2. The glass material according to claim 1, characterized in that It is composed of the following components in percentage by mass: 25%-45% SiO2, 48%-55% PbO, 0.5%-5% Gd2O3, 0.5%-1.5% CeO2, 0.5%-5% Al2O3, 4%-10% Na2O, 6.8%-10% K2O, and 0.1%-3% of an alkaline earth metal oxide selected from at least one of CaO and MgO.

3. The glass material according to claim 1 or 2, characterized in that: The mass percentage of Gd2O3 is 1%-5%.

4. The glass material according to claim 1 or 2, characterized in that: The mass percentage of CeO2 is 0.5%-1.2%.

5. The glass material according to claim 1 or 2, characterized in that: The mass percentage of Al2O3 is 0.5%-3%.

6. The glass material according to claim 1 or 2, characterized in that: The mass percentage of Na2O is 4%-7.3%.

7. The glass material according to claim 1 or 2, characterized in that: The mass percentage of CaO is 0.5%-2%.

8. The glass material according to claim 1 or 2, characterized in that: The mass percentage of MgO is 0-1%.

9. The glass material according to claim 1 or 2, characterized in that: The mass percentage of at least one alkaline earth metal oxide selected from CaO and MgO is 0.5%-2.5%.

10. The glass material according to claim 1, which is composed of the following components in percentage by mass: 25%-45% SiO2, 48%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 4%-7.3% Na2O, 6.8%-10% K2O, and 0.1%-3% of an oxide selected from at least one of CaO and MgO.

11. The glass material according to claim 1, characterized in that It consists of the following components in percentage by mass: 25%-45% SiO2, 48%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 4%-7.3% Na2O, 6.8%-10% K2O, 0.5%-2% CaO and 0-1% MgO.

12. The glass material according to claim 1, characterized in that It consists of the following components in percentage by mass: 25%-45% SiO2, 48%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 4%-7.3% Na2O, 6.8%-10% K2O, 1.5%-2% CaO and 0-1% MgO.

13. The glass material according to claim 1, characterized in that It consists of the following components in percentage by mass: 25%-45% SiO2, 48%-55% PbO, 1%-5% Gd2O3, 0.5%-1.2% CeO2, 0.5%-3% Al2O3, 4%-7.3% Na2O, 6.8%-10% K2O, and 0.5%-2% CaO.

14. The glass material according to claim 1 or 2, characterized in that: When the glass material is 20 mm thick, 60 The shielding rate of Co gamma rays is ≥40.47%; the shielding rate for thermal neutrons is ≥92.63%; the transmittance at 560nm is ≥86.42%, and the transmittance at 560nm after irradiation with a total dose of 10000Gy of gamma rays is ≥82.61%, and the transmittance at 560nm decreases by ≤6.67% after irradiation with a total dose of 10000Gy of gamma rays.

15. A method for preparing the glass material according to any one of claims 1 to 14, comprising: The raw materials are mixed, melted at high temperature, clarified by auxiliary stirring, formed by cooling, and precisely annealed to obtain the product.

16. The method according to claim 15, characterized in that The high temperature melting temperature is 1235-1350°C, the molding temperature is 1108-1222°C, and the annealing temperature is 405-450°C.

17. A radiation shielding material comprising the glass material according to any one of claims 1 to 14. 18 . An optical element comprising the glass material according to claim 1 .

19. The optical element according to claim 18, characterized in that The optical element is a radiation shielding optical window element.

20. Use of the glass material according to any one of claims 1 to 14, the radiation shielding material according to claim 17, or the optical element according to claim 18 or 19 in the field of radiation shielding or the field of optics.

Images