CN117720269B

CN117720269B - Glass material, preparation method thereof and application thereof in radiation shielding field

Info

Publication number: CN117720269B
Application number: CN202311726467.XA
Authority: CN
Inventors: 韩玉; 曹振博; 张梅伦; 杨胜赟; 王可; 李少华; 王乔; 张洋; 周游; 贾金升; 洪升
Original assignee: China Building Materials Photon Technology Co ltd
Current assignee: China Building Materials Photon Technology Co ltd
Priority date: 2023-12-15
Filing date: 2023-12-15
Publication date: 2024-07-09
Anticipated expiration: 2043-12-15
Also published as: CN117720269A

Abstract

The application provides a glass material, a preparation method thereof and application thereof in the field of radiation shielding. The glass material comprises or consists of ：SiO₂45-60%;BaO 0.1-1%;B₂O₃10-20%;CeO₂2-5%;Al₂O₃1-2%;MgO 2.7-5%;NaO₂0-20%;K₂O 9%-15%. components in percentage by mass, wherein the glass material has good shielding performance on alpha rays and beta rays and gamma irradiation resistance, has excellent comprehensive shielding performance, still has excellent permeability, chemical stability and mechanical property after being irradiated by gamma rays for a plurality of times, and is more suitable for practical application.

Description

Glass material, preparation method thereof and application thereof in radiation shielding field

Technical Field

The invention relates to a special glass material, in particular to a glass material, a preparation method thereof and application thereof in the field of radiation shielding.

Background

Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

In the research process of the nuclear field, the radiation shielding window material is the only window for a researcher or an operator to observe the nuclear waste solidification, spent fuel purification and nuclear raw material processing process at one side of an operating room, and is the only means for clearly observing the whole working area in the hot room and the operation of an executing mechanism or a manipulator. In environments with severe radiation contamination, the gamma irradiation dose rate between the hot cell and the operating cell is up to 2 x 10 ⁷ times different. The high-energy electrons in the rays are radiated to the surface of an object, so that the crystal structure of a surface substance is damaged to cause defects, and meanwhile, the ionization and displacement effects generated by high-energy protons and heavy ions can cause the glass material to become black and dark, so that the transmittance of the glass is reduced. In addition, since α rays and β rays exist in a strong radiation environment, the penetration ability of α rays and β rays is weak, but if the α rays and β rays enter human tissues and organs, the energy will be absorbed by the tissues and organs entirely, and the damage to human body is great, so that special attention is paid to preventing the internal irradiation of α rays and β rays, so that the glass closest to the hot chamber side in the irradiation shielding window is required to have good shielding performance for α rays and β rays, and good irradiation resistance for high energy rays/particles, and meanwhile, should have good processability and sealing performance, i.e., high requirements for the comprehensive performance of materials.

However, the existing glass material resistant to high-energy ray irradiation often has poor comprehensive performance, such as poor optical transmittance or irradiation resistance under high-dose gamma radiation, obviously reduced transmittance, chemical stability, mechanical properties (such as strength, hardness and the like) and processability after irradiation, and seriously reduced comprehensive performance of the material.

Disclosure of Invention

Aiming at the defects existing in the prior art, the invention provides the glass material which has high light transmittance, comprehensive radiation shielding capability, excellent irradiation resistance, good shielding performance on alpha rays and beta rays and gamma irradiation resistance, good chemical and mechanical properties, easy processing and good sealing performance, so as to meet the strict requirements on a shielding window in the field of nuclear industry. Meanwhile, the glass material has excellent permeability, chemical stability and mechanical property after being irradiated by gamma rays for a plurality of times, and is more suitable for practical application. The material may have wide application foreground in space flight, nuclear medicine and other fields.

Specifically, the present invention provides the following technical features, and one or more of the following technical features are combined to form the technical scheme of the present invention.

In a first aspect of the present invention, there is provided a glass material comprising, in mass percent, the following components ：SiO₂45-60%;BaO 0.1-1%;B₂O₃10-20%;CeO₂2-5%;Al₂O₃1-2%;MgO 2.7-5%;NaO₂0-20%;K₂O 9%-15%.

In a preferred embodiment, the glass material according to the invention comprises, in mass percent, ：SiO₂45-60%;BaO 0.1-1%;B₂O₃10-20%;CeO₂2-5%;Al₂O₃1-2%;MgO 2.7-5%;NaO₂0-20%;K₂O 9%-15%, of the following components, the sum of the mass percent of the components being 100%.

In an embodiment of the present invention, siO ₂ is used as a main component of the glass to provide a stable structural skeleton. When the SiO ₂ content is too high, the melting point of the glass may be too high, and the processing difficulty is increased; while too low a content may result in an insufficiently stable structure, reducing the mechanical strength and chemical stability of the glass. The addition of B ₂O₃ improves the thermal stability and the chemical stability, reduces the high-temperature viscosity, and participates in a skeleton network together with SiO ₄ to strengthen the network stability. However, the content of B ₂O₃ needs to be strictly controlled to avoid damaging the network structure, for example, when B ₂O₃ is excessive, part B ₂O₃ cannot form BO ₄, only in the form of triangular body BO ₃, which can damage the skeleton structure of the network, so that the firm and compact unified network is relatively reduced, and the chemical stability of the glass is reduced; However, the insufficient content of B ₂O₃ cannot fully exert the effect of improving the thermal stability. In some embodiments of the present invention, the content of SiO ₂ is 45-60% and the content of B ₂O₃ is 10-20% by mass. Further preferably, the content of SiO ₂ is 50-60%, preferably 56-60%, more preferably 59-60%, and the content of SiO ₂ may also be selected from the following: 52-60%,59.9-60%,45-59.9%,45-56%,45-52%,52-59.9%,52-56%, 56-59.9%. Further preferably, the content of B ₂O₃ is 10-18%, preferably 10-17%, and, The content of B ₂O₃ can also be chosen from the following ：10-10.1%,10-10.3%,10.1-20%,10.1-18%,10.1-17%,10.1-10.3%,10.3-20%,10.3-18%,10.3-17%,17-20%,18-20%,17-18%. within the above-mentioned content ranges of SiO ₂ and B ₂O₃, in particular, in the preferred content range, a structural basis is provided for obtaining good thermal stability, chemical stability and mechanical strength of the glass material, and simultaneously, the thermal expansion coefficient, softening temperature and the like of the material are improved. In particular, in some embodiments of the present invention, when the content of SiO ₂ is not less than 2.6 times the content of B ₂O₃, the synergistic effect of SiO ₂ and B ₂O₃ can be better exerted.

In an embodiment of the invention, the glass material further comprises 0-20% of NaO ₂ and 9-15% of K ₂ O. The incorporation of K ₂ O and/or Na ₂ O in these proportions in SiO ₂ and B ₂O₃ helps to form a uniform and consistent glass, Oxygen atoms in K ₂ O and/or Na ₂ O can enter unoccupied orbitals of the B outer layer, so that the electron orbitals of the outermost layer of the boron atoms recombine, promote the conversion of BO ₃ (boron-oxygen triangle) to BO ₄ (boron-oxygen tetrahedron), The structure of B is converted from a planar layered structure to a three-dimensional framework structure, and a basic condition is further provided for the fusion of SiO ₂ and B ₂O₃ into a uniform glass matrix. Meanwhile, K ₂ O and/or Na ₂ O can play a role in fluxing, accelerate the melting and clarifying processes of the glass, the mixed alkali effect of K ₂ O and Na ₂ O can reduce the surface tension of the glass, Meanwhile, the doping of K ⁺ and/or Na ⁺ ions is beneficial to the optimization of the glass structure, so that the mechanical properties of the glass are improved. The balance of the proportion of the K ₂ O and/or the Na ₂ O is critical to maintaining the chemical stability and the mechanical strength of the glass, the excessive content of the K ₂ O and/or the Na ₂ O can reduce the chemical stability and the mechanical strength of the glass, while insufficient results in an inability to effectively lower the melting point and improve the processability. in some embodiments of the present invention, the content of K ₂ O is further 9-13.5%, preferably 9.6-13.5%, more preferably 9.6-12% by mass, and the content of K ₂ O may also be selected from the following ：9-13.1%,9-12%,9-11.3%,9-11%,9-10%,9-9.6%,9.6-15%,9.6-13.1%,9.6-11.3%,9.6-11%,9.6-10%,10-15%,10-13.5%,10-13.1%,10-12%,10-11.3%,10-11%; in some embodiments of the present invention, The content of NaO ₂ is further 0-15% or 10-20%, preferably 0-12%, more preferably 10-12% or 0% by mass; The method comprises the steps of, The content of NaO ₂ may also be selected from ：0-14.2%,0-13.2%,0-10.4%,0-10%,10-20%,10-15%,10-14.2%,10-13.2%,10-10.4%,10.4-20%,10.4-15%,10.4-14.2%,10.4-13.2%,10.4-12%,12-20%,12-15%,12-14.2%,12-13.2%,13.2-20%,13.2-15%,13.2-14.2%,14.2-20%,14.2-15%. within the above-mentioned range of K ₂ O and/or Na ₂ O content, In particular, in the preferred content range, the glass material is further ensured to obtain proper melting point, good processability, mechanical property and chemical stability. in particular, in some embodiments of the present invention, when the K ₂ O content is not less than 0.8 times the Na ₂ O content, the synergistic effect of SiO ₂ and B ₂O₃ is further promoted, And better balances the chemical stability and mechanical strength of the glass material.

In an embodiment of the present invention, baO is further introduced into the glass material in an amount of 0.1 to 1% by mass. The introduction of the BaO content can provide free oxygen, promote glass melting and improve glass fiber drawing, and simultaneously is helpful for slowing down the speed of radiation ions, has ray capturing capability, can reduce the probability of damaging a glass structure and enhances the radiation resistance of a glass material. However, it should be noted that BaO may be introduced to provide better radiation resistance, but may also affect the chemical stability of the glass material, particularly when the content is too high, the chemical stability of the glass material may be significantly reduced, while a lower content may result in insufficient radiation resistance, and a lower content may result in insufficient radiation resistance. On the basis, ceO ₂ with the mass percent of 2-5% is also introduced into the glass material. The CeO ₂ with the content can effectively generate color centers under the radiation environment, improve the radiation resistance stability, has good ultraviolet absorption capacity, is beneficial to clarification, reduces the generation of glass defects, can exert synergistic and complementary effects with 0.1-1% of BaO, is beneficial to improving the transmittance and enhancing the radiation resistance, well realizes the balance between the transmittance and the radiation resistance, and simultaneously avoids the adverse effect on the chemical stability caused by the introduction of the BaO. however, it should be noted that CeO ₂ should not be too high, for example, above 1%, but rather would significantly reduce the transmittance of the glass material. In an embodiment of the present invention, a range of suitable BaO and CeO ₂ contents are provided. for example, in some embodiments of the present invention, the content of BaO is 0.2 to 1%, preferably 0.3 to 1%, more preferably 0.1 to 0.4%, still more preferably 0.1 to 0.3% or 0.3 to 0.4% by mass, and may also be selected from ：0.1-0.9%,0.1-0.5%,0.1-0.4%,0.1-0.2%,0.2-1%,0.2-0.9%,0.2-0.5%,0.2-0.4%,0.2-0.3%,0.3-1%,0.3-0.9%,0.3-0.5%,0.4-1%,0.4-0.9%,0.4-0.5%,0.5-1%,0.5-0.9%,0.9-1%. in some embodiments of the present invention, the content of CeO ₂ is 2.5 to 5% by mass, Preferably 2.5 to 4% or 4 to 5%, and the content of CeO ₂ may also be selected from ：2-4%,2-3%,2-2.7%,2-2.6%,2-2.5%,2-2.3%,2-2.1%,2.1-5%,2.1-4%,2.1-3%,2.1-2.7%,2.1-2.6%,2.1-2.5%,2.1-2.3%,2.3-5%,2.3-4%,2.3-3%,2.3-2.7%,2.3-2.6%,2.3-2.5%,2.5-3%,2.5-2.7%,2.5-2.6%,2.6-5%,2.6-4%,2.6-3%,2.6-2.7%,2.7-5%,2.7-4%,2.7-3%,3-5%,3-4%. below in the above-mentioned content ranges of BaO and CeO ₂, especially in the preferred content ranges, to be able to well balance the radiation resistance and transmittance of the glass material, And further stabilize the chemical capabilities of the material. In particular, in some embodiments of the present invention, the content of CeO ₂ should be not less than 2.7 times the content of BaO, which can better exert the synergistic and complementary effects of CeO ₂ and BaO.

In the embodiment of the invention, al ₂O₃ and MgO are also introduced at the same time and are used as structure adjusting oxides, and the structure adjusting oxides are used for reducing the crystallization tendency and the thermal expansion coefficient of the glass and improving the thermal stability; at the same time, their introduction is also used in the present invention to enhance the chemical stability and mechanical strength of the glass. It should be noted, however, that the use of Al ₂O₃ and MgO requires control of the content to avoid negative effects on glass flowability and the like and to reduce manufacturing costs. For example, when the content of Al ₂O₃ is too high, the viscosity of the glass liquid is increased, which makes melting and refining difficult, but increases the crystallization tendency, for example, when the content of MgO is too high, the glass properties are adversely affected, the crystallization tendency of the glass is increased, and the annealing temperature is increased, thereby increasing the manufacturing cost. Therefore, in the embodiment of the present invention, the content of Al ₂O₃ should be controlled to be 1-2% by mass and the content of MgO should be controlled to be 2.7-5% by mass. Also provided in embodiments of the present invention are a range of suitable Al ₂O₃ and MgO contents. For example, in some embodiments of the invention, the Al ₂O₃ is present in an amount of 1 to 1.5%, preferably 1 to 1.4%, more preferably 1 to 1.1% and or 1.4 to 1.5% by mass; and, the content of Al ₂O₃ may also be selected from the following: 1-1.2%,1.1-2%,1.1-1.5%,1.1-1.4%,1.2-2%,1.2-1.5%,1.2-1.4%,1.4-2%,1.4-1.5%,1.5-2%. In some embodiments of the invention, the MgO content is 2.7-4%, preferably 2.7-3.9%, more preferably 2.7-3.4% or 3.4-5% by mass; and, the MgO content may also be selected from the following: 2.7-3%,2.7-3.3%,3.3-5%,3.5-4%,3.3-3.9%,3.3-3.4%,3.4-5%,3.4-4%,3.4-3.9%,3.9-5%,3.9-4%. In particular, in some embodiments of the present invention, the content of CeO ₂ should be not less than 2.7 times the content of BaO. This can better exert the synergistic effect of Al ₂O₃ and MgO.

In some embodiments of the present invention, the glass material of the present invention comprises, in mass percent, ：SiO₂45-60%;BaO 0.1-1%;B₂O₃10-18%;CeO₂2-5%;Al₂O₃1-1.5%;MgO 2.7-5%;NaO₂0-20%;K₂O 9%-13.1%,, the sum of the mass percent of the components of the following composition being 100%.

In some embodiments of the present invention, the glass material of the present invention comprises, in mass percent, ：SiO₂45-60%;BaO 0.3-1%;B₂O₃10-17%;CeO₂2.1-5%;Al₂O₃1-1.5%;MgO 2.7-5%;NaO₂0-12%;K₂O 9%-13.1%,, the sum of the mass percent of the components of the following composition being 100%.

In some embodiments of the present invention, the glass material of the present invention comprises, in mass percent, ：SiO₂45-60%;BaO 0.3-1%;B₂O₃10-17%;CeO₂2.7-5%;Al₂O₃1-1.4%;MgO 2.7-3.4%;NaO₂10-12%;K₂O 9.6%-11%,, the sum of the mass percent of the components of the following composition being 100%.

In some embodiments of the present invention, the glass material of the present invention comprises, in mass percent, ：SiO₂59-60%;BaO 0.3-1%;B₂O₃10-17%;CeO₂2.7-5%;Al₂O₃1-1.4%;MgO 2.7-3.4%;NaO₂10-12%;K₂O 9.6%-11%,, the sum of the mass percent of the components of the following composition being 100%.

The invention prepares the glass with uniform inner quality and stable components by adjusting the contents of SiO ₂、B₂O₃、Na₂ O and K ₂ O, and has good mechanical stability, and on the basis, the transmittance and the irradiation resistance of the glass are balanced by controlling BaO, ceO ₂ and the like, so that the glass has good shielding performance on alpha rays and beta rays and excellent gamma irradiation resistance, has excellent comprehensive shielding performance, and also has good optical transmittance, and the contents of Al ₂O₃ and MgO are further introduced and controlled, so that the crystallization tendency and the thermal expansion coefficient of the glass are reduced, the thermal stability is improved, and meanwhile, the chemical stability and the mechanical strength of the glass are further enhanced. The combination of the components also reduces the viscosity of glass melting, reduces the difficulty of glass forming, reduces the surface tension of the glass, improves the mechanical property and the sealing property of the glass, and is beneficial to processing and manufacturing. The glass material obtained by the coordination of the components has good shielding performance and gamma irradiation resistance to alpha rays and beta rays, particularly has excellent permeability, chemical stability and mechanical property after being irradiated by gamma rays for a plurality of times, is easy to process and manufacture, and is more suitable for practical application.

In a second aspect of the present invention, there is provided a method of preparing a glass material as described in the first aspect above, comprising: mixing the raw materials in proportion, melting at high temperature, stirring, clarifying at high temperature, and forming to obtain the glass material.

In one embodiment of the invention, the method comprises:

S1, mixing glass components including quartz sand, boric acid, alkali metal and/or alkaline earth metal salts in proportion, adding a clarifying agent in proportion, and uniformly mixing;

S2, melting the mixture at high temperature and stirring;

S3, stirring, clarifying and forming at high temperature to obtain the glass material.

In some embodiments of the invention, the alkali metal and/or alkaline earth metal salts are carbonates and/or nitrates.

In some embodiments of the invention, the high temperature melting temperature is 1360-1450 ℃ and the melting time is 9-30 h.

In some embodiments of the invention, the agitation speed is 10-40 r/min and the agitation time is 10-14 h. The method has certain requirements on the uniformity of the feed liquid before glass forming, so that the feed liquid of the glass before forming needs to be stirred for a period of time at a certain rotating speed, so that the uniformity and clarity of the feed liquid are improved, when the uniformity of the feed liquid is low, the feed liquid is easy to generate layering or agglomeration, the melting, clarifying and homogenizing of the glass are difficult, even stripe or stone defects can be generated when serious, the formed glass contains bubbles due to low clarity of the feed liquid, and the quality of the glass is reduced.

In some embodiments of the invention, the molding temperature is 1060-1150 ℃ and the molding time is 5-25 min. The generation of secondary bubbles and impurities is prevented by rapid molding of glass.

In a third aspect of the present invention, there is provided an optical element comprising or made of the glass material described in the first aspect above;

in some embodiments of the invention, the optical element may shield gamma rays, alpha rays, and beta rays.

In a fourth aspect of the present invention, there is provided a radiation shielding material comprising or made of the glass material described in the first aspect above;

in some embodiments of the invention, the radiation shielding material is used to shield gamma rays, alpha rays and beta rays;

In some embodiments of the invention, the radiation shielding material is a radiation shielding window material.

In a fourth aspect of the present invention there is provided the use of a glass material as described in the first aspect above or an optical element as described in the third aspect above or a radiation shielding material as described in the fourth aspect above in the optical field or in the radiation shielding field.

In some embodiments of the invention, the radiation shielding field or the optical field is selected from the group consisting of the nuclear industry field, the nuclear medicine field and the space exploration field.

In some embodiments of the invention, the application is for use as a radiation shielding window material.

The specific features described in the above embodiments of the present invention may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

The numerical ranges recited herein include all numbers within the range and include any two values within the range, unless specifically stated otherwise. For example, 0.3-1%, which includes all values between 0.3-1%, and which includes values (0.31-0.99%) of the range consisting of any two values (e.g., 0.31%, 0.99%) within the range; the different values of the same index appearing in all embodiments of the invention can be combined arbitrarily to form a range value.

Through one or more of the above technical means, the following beneficial effects can be achieved:

the glass material provided by the invention comprises the following components: high transmittance, high chemical stability, good shielding performance for alpha rays and beta rays, high-energy ray irradiation resistance and good mechanical properties. The glass material provided by the invention has the maximum transmittance of more than or equal to 90.3% and the minimum transmittance of more than or equal to 70.1% in the range of 400-800 nm before being irradiated, and has the maximum transmittance of more than or equal to 88.1% and the minimum transmittance of more than or equal to 53.8% in the range of 400-800 nm after being irradiated by gamma rays with high dose of 1X 10 ⁶ Gy. The glass has small change of transmittance and mechanical strength before and after irradiation and almost no change of chemical stability, which indicates that the glass has good irradiation resistance. In particular, the glass of the invention can still have good transmittance, chemical stability and mechanical strength after multiple times of irradiation, for example, in the embodiment of the invention, the transmittance of the glass of the invention is still higher than 87% in the range of 400-800 nm after 3 times of 1X 10 ⁶ Gy high-dose gamma ray irradiation.

The glass material provided by the invention has proper melting temperature (1360-1450 ℃), good crystallization resistance, good mechanical property, easy molding and easy processing and manufacturing.

The transmittance of the existing glass in a wide wavelength range is not high, and meanwhile, after the glass material is irradiated by high-intensity high-energy rays, color centers are easy to generate, so that the transmittance of the glass material is influenced. The invention prepares the irradiation-resistant glass with high transmittance and high chemical stability by selecting and adjusting the comprehensive proportion of BaO, ceO ₂、Al₂O₃, mgO and other components, and the irradiation-resistant glass still maintains higher transmittance after being irradiated by gamma rays with high dose for multiple times.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Embodiments of the present application are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 is a schematic diagram of an optical glass turbidity measuring device for testing the moisture resistance stability of glass, wherein: 1 is a light source; 2 is a collimator; 3 is a sample; 4 is an integrating sphere; 5 is a photodetector; 6 is an optical trap; 7 is a standard whiteboard.

FIG. 2 is a graph of transmittance contrast between 400 and 800 nm before and after exposure to gamma rays of 1X 10 ⁶ Gy for a glass article of the invention and a comparative glass article.

FIG. 3 is a graph of maximum transmittance of a glass article of the present invention versus a comparative glass article, each irradiated 3 times (each irradiation dose 1X 10 ⁶ Gy) by gamma-ray cycles, in the range of 400-800 nm before and after each irradiation.

Detailed Description

The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present application may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present application. The preferred methods and materials described herein are presented for illustrative purposes only. In the present application, the weight percent (weight percent) and the mass percent (mass percent) represent the same meaning, representing the proportion of a certain component in a mixture, calculated by dividing the mass of the component by the total mass of the whole mixture and then multiplying by 100%, expressed in wt%.

The performance parameters in the following examples were measured as follows:

The coefficient of thermal expansion of the glass samples was measured using a model DIL 402 coefficient of expansion tester, available from the refractory company, germany. Sample preparation, the glass sample was ground and polished to a cylindrical glass strip of Φ6x50 mm with the two end faces parallel. The temperature rising speed is set to be 5 ℃/min, and the data acquisition period is set to be 20 ms. And drawing a relation curve of the temperature and linear expansion by the data, and obtaining the glass transition temperature and the expansion softening temperature by a tangent method. (GB/T7962.16 to 2010)

Transmittance was measured with an ultraviolet-visible infrared spectrophotometer.

Acid resistance stability test: as the measurement medium, a solution having an acidity of pH2.9, pH4.6 and pH6.0 was used. After the surface of the polished glass sample is corroded by a measuring medium, observing the time for which the surface of the glass has purple-blue interference color or the surface of the glass has variegated or falls off under an incandescent lamp, and carrying out descending classification on the acid-resistant stability of the colorless optical glass according to the time. (GB/T7962.14 to 2010)

Glass moisture resistance stability test: the turbidity values H ₀ and H ₁ before and after the corrosion of the sample to be measured and the standard sample (BaK glass and ZK9 glass) were measured respectively using the apparatus shown in fig. 1, calculated from h=h ₁-H₀, and the moisture resistance stability rating of the optical glass was obtained by looking up a table based on the comparison with the turbidity values of the standard sample. (GB/T7962.15 to 2010)

Glass bending strength test: the bending strength (GB/T37781-2019) of the sample is obtained by measuring the width b and the thickness d of the middle part of the sample, the distance L between two sample holders and the maximum load P when the sample breaks, and substituting the following materials:

wherein, The bending strength of the sample is expressed in megapascals (MPa); p is the maximum load of the sample at break, in newtons (N); b is the sample width in millimeters (mm); d is the sample thickness in millimeters (mm).

Glass hardness test: applying a certain load to a quadrangular pyramid diamond pressure head with symmetrical edges of 172 degrees and 130 degrees to vertically press the quadrangular pyramid diamond pressure head on the surface of a sample, removing the load after the sample is kept for a certain time, observing and measuring the length of the long diagonal line of the indentation on the sample by using a microscope, converting the projection area of the indentation, and substituting the projection area into the following formula to calculate the Kjeldahl hardness H _K (GB/T7962.18-2010):

Wherein F is a pressing load, and the unit is Newton (N); d is the length of the long diagonal of the indentation in millimeters (mm); h _K is Kjeldahl hardness in 10 ⁷ Pa (10 ⁷ Pa).

The invention will be further illustrated with reference to specific examples.

Example 1

The components and weight percentages of the components of the glass material of this example are shown in Table 1, and the physical properties are shown in Table 2.

The preparation method comprises the following steps: quartz sand, boric acid, aluminum hydroxide, potassium carbonate, sodium carbonate, barium oxide, aluminum oxide and magnesium oxide are taken as raw materials, a clarifying agent CeO ₂ is added, the weight of the clarifying agent accounts for 5.0 percent of the weight of the glass, after the materials are fully mixed, the materials are melted at 1360 ℃ to form 9 h, mechanically stirred (10 r/min,10 h), assisted to be clarified at high temperature, and leaked or cast to be molded at 1060 ℃ for 5 min.

Example 2

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 3.0% of the weight of the glass; the melting temperature is 1400 ℃, and the melting time is 17 h; mechanical stirring (25 r/min,13 h), molding temperature 1100 ℃, molding time 15 min, other preparation steps and parameters were the same as in example 1.

Example 3

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 2.3% of the weight of the glass; the melting temperature is 1450 ℃, and the melting time is 30 h; mechanical stirring (40 r/min,14 h), molding temperature 1150 ℃, molding time 25 min, other preparation steps and parameters were the same as in example 1.

Example 4

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 2.0% of the weight of the glass; the melting temperature is 1390 ℃, and the melting time is 20 h; mechanical stirring (20 r/min,12 h), forming temperature 1080 ℃, forming time 15 min, other preparation steps and parameters were the same as in example 1.

Example 5

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 2.1% of the weight of the glass; the melting temperature is 1420 ℃, and the melting time is 25 h; mechanical stirring (35 r/min,14 h), molding temperature 1100 ℃, molding time 25 min, other preparation steps and parameters were the same as in example 1.

Example 6

In the preparation method, the clarifying agent is CeO ₂, and the weight of the clarifying agent accounts for 3.0% of the weight of the glass; the melting temperature is 1410 ℃, and the melting time is 17 h; mechanical stirring (25 r/min,13 h), molding temperature 1100 ℃, molding time 20min, other preparation steps and parameters were the same as in example 1.

Example 7

The components and weight percentages of the components of the glass material of this example are shown in Table 1, and the physical properties are shown in Table 2. The preparation method is the same as in example 1.

Example 8

Example 9

The components and weight percentages of the components of the glass material of this example are shown in Table 1, and the physical properties are shown in Table 2. In the preparation method, the clarifying agent is CeO ₂, the weight of the clarifying agent accounts for 2.6 percent of the weight of the glass, and other preparation steps and parameters are the same as in example 1.

Comparative examples 1 to 8

The components and weight percentages of the components of the glasses of comparative examples 1 to 8 are shown in Table 3, and the physical properties are shown in Table 4.

The glass preparation steps and parameters of comparative examples 1 to 8 were the same as those of example 1.

TABLE 1 Components, content and physical Properties of the glass materials according to examples 1 to 9 of the present invention

TABLE 2 physical Properties of the glass materials according to examples 1 to 9 of the invention

TABLE 3 Components, content and physical Properties of the glass materials described in comparative examples 1 to 8

Table 4 physical Properties of the glass materials described in comparative examples 1 to 8

Ts in tables 2 and 4 are softening points, i.e., temperatures at which glass viscosities reach 10 ^7.6 dPa.s; alpha _30-300℃ is the coefficient of thermal expansion of the glass measured in the range of 30-300 ℃; the irradiation is gamma ray irradiation with the irradiation dose of 1X 10 ⁶ Gy.

Examples 1-9 the optical transmittance and irradiation resistance of the glass were better by reasonably adding the corresponding components and adjusting the proportions of the components in the raw materials. As can be seen from Table 2, the optical transmittance of the glasses produced in examples 1 to 9 of the present invention is as follows: before irradiation, the maximum transmittance is more than or equal to 90.2 percent and the minimum transmittance is more than or equal to 70.1 percent in the range of 400-800 nm. After one irradiation of 1X 10 ⁶ Gy, the maximum transmittance is more than or equal to 84.4 percent and the minimum transmittance is more than or equal to 53.2 percent in the range of 400-800 nm. In particular, the glass of the present invention still has good transmittance, chemical stability and mechanical properties after multiple irradiation, such as the glass of example 1, and the maximum transmittance of 400-800 nm is still higher than 87% after the magnetic irradiation of 3 gamma rays (see fig. 1 and 2). The glasses prepared in examples 1-9 were superior in transmittance, chemical stability and irradiation resistance to the glasses involved in comparative examples, while having good mechanical properties and being easy to manufacture.

From the above, it can be seen that the high transmittance and high chemical stability high energy ray irradiation resistant glass provided in examples 1 to 9 of the present invention has excellent optical transmittance, chemical stability and good irradiation resistance. The specific features described in the above embodiments of the present invention may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

The glass material has the advantages of higher optical transmittance, good chemical stability, excellent irradiation resistance, good processability and sealing performance, and good comprehensive performance, can be used as a main material of a radiation shielding window, can be applied to other high-energy irradiation environments such as aviation, aerospace, medicine and the like, and has wide application prospect.

The foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A glass material, which consists of ：SiO₂56-60%;BaO 0.1-1%;B₂O₃ 10-18%;CeO₂ 2-5%;Al₂O₃ 1-2%;MgO 2.7-5%;Na₂O 10-15%;K₂O 9%-15%; parts by mass of a component in which the content of SiO ₂ is not less than 2.6 times the content of B ₂O₃; the content of K ₂ O is not less than 0.8 times of the content of Na ₂ O; the content of CeO ₂ is not less than 2.7 times of the content of BaO.

2. The glass material according to claim 1, wherein the content of SiO ₂ is 59 to 60% by mass.

3. The glass material according to claim 1, wherein the content of BaO is 0.2 to 1% by mass.

4. The glass material according to claim 1, wherein the content of BaO is 0.3 to 1% by mass.

5. The glass material according to claim 1, wherein the content of BaO is 0.1 to 0.4% by mass.

6. The glass material according to claim 1, wherein the content of BaO is 0.1 to 0.3% or 0.3 to 0.4% by mass.

7. The glass material according to claim 1, wherein the content of B ₂O₃ is 10 to 17% by mass.

8. The glass material according to claim 1, wherein the content of CeO ₂ is 2.5 to 5% by mass.

9. The glass material according to claim 1, wherein the content of CeO ₂ is 2.5 to 4% or 4 to 5% by mass.

10. The glass material according to claim 1, wherein the content of Al ₂O₃ is 1 to 1.5% by mass.

11. The glass material according to claim 1, wherein the content of Al ₂O₃ is 1 to 1.4% by mass.

12. The glass material according to claim 1, wherein the content of Al ₂O₃ is 1 to 1.1% or 1.4 to 1.5% by mass.

13. The glass material according to claim 1, wherein the content of MgO is 2.7 to 4% by mass.

14. The glass material according to claim 1, wherein the content of MgO is 2.7 to 3.9% by mass.

15. The glass material according to claim 1, wherein the content of MgO is 2.7 to 3.4% by mass.

16. The glass material according to claim 1, wherein the content of Na ₂ O is 10 to 12% by mass.

17. The glass material according to claim 1, wherein the content of K ₂ O is 9 to 13.5% by mass.

18. The glass material according to claim 1, wherein the content of K ₂ O is 9.6 to 13.5% by mass.

19. The glass material according to claim 1, wherein the content of K ₂ O is 9.6 to 12% by mass.

20. The glass material according to claim 1, wherein the sum of the mass percentages of the components ：SiO₂ 56-60%;BaO 0.1-1%;B₂O₃ 10-18%;CeO₂ 2-5%;Al₂O₃ 1-1.5%;MgO 2.7-5%;Na₂O 10-15%;K₂O 9%-13.1%, is 100% as a mass percentage.

21. The glass material according to claim 1, wherein the sum of the mass percentages of the components ：SiO₂ 56-60%;BaO 0.3-1%;B₂O₃ 10-17%;CeO₂ 2.1-5%;Al₂O₃ 1-1.5%;MgO 2.7-5%;Na₂O 10-12%;K₂O 9%-13.1%, is 100% as a mass percentage.

22. The glass material according to claim 1, wherein the sum of the mass percentages of the components ：SiO₂ 56-60%;BaO 0.3-1%;B₂O₃ 10-17%;CeO₂ 2.7-5%;Al₂O₃ 1-1.4%;MgO 2.7-3.4%;Na₂O 10-12%;K₂O 9.6%-11%, is 100% as a mass percentage.

23. The glass material according to claim 1, wherein the sum of the mass percentages of the components ：SiO₂ 59-60%;BaO 0.3-1%;B₂O₃ 10-10.3%;CeO₂ 2.7-5%;Al₂O₃ 1-1.4%;MgO 2.7-3.4%;Na₂O 10-12%;K₂O 9.6%-11%, is 100% as a mass percentage.

24. A method of making the glass material of any of claims 1 to 23, comprising: mixing the raw materials in proportion, melting at high temperature, stirring, clarifying at high temperature, and forming to obtain the glass material.

25. The method according to claim 24, characterized in that the method comprises:

Mixing glass components including quartz sand, boric acid, alkali metal and/or alkaline earth metal salts in proportion, adding a clarifying agent in proportion, and uniformly mixing;

Melting the mixture at high temperature, and stirring;

and stirring, clarifying and forming to obtain the glass material.

26. The method according to claim 25, wherein the alkali and/or alkaline earth metal salts are carbonates and/or nitrates.

27. The method of claim 24 or 25, wherein the high temperature melting is at 1360-1450 ℃ and the melting time is 9-30 h.

28. The method of claim 24 or 25, wherein the stirring speed is 10-40 r/min and the stirring time is 10-14 h.

29. The method of claim 24 or 25, wherein the molding is performed at a temperature of 1060-1150 ℃ for a time of 5-25 min.

30. An optical element comprising or made of the glass material of any one of claims 1 to 23.

31. The optical element of claim 30, wherein the optical element is shielded from gamma rays, alpha rays, and beta rays.

32. A radiation shielding material comprising or made of the glass material of any one of claims 1 to 23.

33. The radiation shielding material of claim 32, wherein the radiation shielding material is configured to shield gamma rays, alpha rays, and beta rays.

34. The radiation shielding material of claim 33, wherein the radiation shielding material is a radiation shielding window material.

35. Use of the glass material of any one of claims 1 to 23 or the optical element of claim 30 or 31 or the radiation shielding material of any one of claims 32 to 34 in the optical field or in the radiation shielding field.

36. The use according to claim 35, wherein the use is as a radiation shielding window material.

37. The use according to claim 35, wherein the radiation shielding field or the optical field is selected from the group consisting of the nuclear industry field, the nuclear medicine field and the space exploration field.