Glass material, and preparation method therefor and use thereof in field of radiation shielding

Abstract

A glass material, and a preparation method therefor and the use thereof in the field of radiation shielding. The glass material comprises or consists of the following components in percentages by mass: 45-60% of SiO2; 0.1-1% of BaO; 10-20% of B2O3; 2-5% of CeO2; 1-2% of Al2O3; 2.7-5% of MgO; 0-20% of Na2O; and 9-15% of K2O. The glass material has good performance of shielding α-rays and β-rays, good gamma irradiation resistance and excellent comprehensive shielding performance, still has good transmission, chemical stability and mechanical performance after being irradiated by high-dose gamma rays multiple times, and is more suitable for practical application.

Description

A glass material and its preparation method and application in the field of radiation shielding Technical Field

[0001] The present invention relates to a special glass material, in particular to a glass material and a preparation method thereof and application in the field of radiation shielding. Background Art

[0002] 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.

[0003] During nuclear research, radiation shielding window materials are the only window for researchers or operators to observe the solidification of nuclear waste, purification of spent fuel, and processing of nuclear materials from one side of the operating room. They are also the only means to clearly observe the entire working area within the hot chamber and the operation of actuators or manipulators. In some environments with severe radiation contamination, the difference in gamma irradiation dose rate between the hot chamber and the operating room can be as high as 2×10 7 times. When high-energy electrons in the radiation are radiated to the surface of an object, they will destroy the crystal structure of the surface material and cause defects. At the same time, the ionization and displacement effects produced by high-energy protons and heavy ions will cause the glass material to become black and dark, thereby reducing the transmittance of the glass. In addition, due to the presence of α rays and β rays in a strong radiation environment, α rays and β rays have weak penetrating power, but if they enter human tissues and organs, their energy will be completely absorbed by the tissues and organs, causing great harm to the human body. Therefore, special attention should be paid to preventing internal irradiation of α rays and β rays. Therefore, the glass on the side closest to the hot chamber in the radiation shielding window is required to have good shielding performance against α rays and β rays, good radiation resistance against high-energy rays / particles, and good machinability and sealing properties, that is, high requirements are placed on the comprehensive performance of the material.

[0004] However, existing glass materials that are resistant to high-energy radiation often have poor overall performance. For example, they do not have good optical transmittance or have poor radiation resistance under high-dose gamma radiation. After irradiation, the transmittance, chemical stability, mechanical properties (such as strength and hardness) and processability decrease significantly, and the overall performance of the material declines seriously.

[0005] Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention provides a glass material that combines high light transmittance, comprehensive radiation shielding capabilities, excellent radiation resistance, strong shielding against alpha and beta rays, and good resistance to gamma radiation. It also possesses excellent chemical and mechanical properties, is easy to process, and exhibits excellent sealing properties. This material meets the stringent requirements for shielded windows in the nuclear industry. Furthermore, after multiple high-dose gamma ray irradiation exposures, this glass material maintains excellent light transmittance, chemical stability, and mechanical properties, making it more suitable for practical applications. This material also has broad application prospects in fields such as aerospace and nuclear medicine.

[0007] Specifically, the present invention provides the following technical features, and the combination of one or more of the following technical features constitutes the technical solution of the present invention.

[0008] In a first aspect of the present invention, a glass material is provided, which comprises the following components, in terms of mass percentage: SiO2 45-60%; BaO 0.1-1%; B2O3 10-20%; CeO2 2-5%; Al2O3 1-2%; MgO 2.7-5%; NaO2 0-20%; and K2O 9%-15%.

[0009] In a preferred embodiment, the glass material of the present invention is composed of the following components, calculated by mass percentage: SiO2 45-60%; BaO 0.1-1%; B2O3 10-20%; CeO2 2-5%; Al2O3 1-2%; MgO 2.7-5%; NaO2 0-20%; and K2O 9%-15%, where the sum of the mass percentages of the individual components is 100%.

[0010] In an embodiment of the present invention, SiO2 serves as the main component of the glass, providing a stable structural skeleton. When the SiO2 content is too high, the melting point of the glass may be too high, increasing the difficulty of processing; while if the content is too low, the structure may be unstable, reducing the mechanical strength and chemical stability of the glass. The addition of B2O3 improves thermal stability and chemical stability, reduces high-temperature viscosity, and participates in the skeleton network together with SiO4 to enhance network stability. However, the content of B2O3 needs to be strictly controlled to avoid destroying the network structure. For example, when B2O3 is excessive, some B2O3 can no longer form BO4 and can only exist in the network in the form of triangular BO3, which will in turn destroy the skeleton structure of the network, reduce the firm, tight and unified network, and reduce the chemical stability of the glass; and insufficient B2O3 content cannot fully play its role in improving thermal stability. In some embodiments of the present invention, the content of SiO2 is 45-60% and the content of B2O3 is 10-20% by weight. More preferably, the content of SiO2 is 50-60%, preferably 56-60%, more preferably 59-60%, and the content of SiO2 can 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%. More preferably, the content of B2O3 is 10-18%, preferably 10-17%, and the content of B2O3 can also be selected 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%. The above-mentioned SiO2 and B2O3 content ranges, especially within the preferred content ranges, provide a structural foundation for the glass material to achieve excellent thermal stability, chemical stability, and mechanical strength, while also improving the material's thermal expansion coefficient, softening temperature, etc. In particular, in some embodiments of the present invention, when the SiO2 content is not less than 2.6 times the B2O3 content, the synergistic effect of SiO2 and B2O3 can be better exerted.

[0011] In an embodiment of the present invention, the glass material further contains 0-20% by mass of NaO2 and 9%-15% by mass of K2O. Introducing K2O and / or Na2O in this proportion into SiO2 and B2O3 helps to form a uniform glass. The oxygen atoms in K2O and / or Na2O can enter the unoccupied orbits of the outer layer of B, causing the outermost electron orbits of the boron atoms to recombine, promoting the transformation of BO3 (boron oxygen triangle) to BO4 (boron oxygen tetrahedron), resulting in the structure of B changing from a planar layered structure to a three-dimensional skeleton structure, further providing the basic conditions for the fusion of SiO2 and B2O3 into a uniform glass matrix. At the same time, K2O and / or Na2O can play a role in fluxing, accelerating the melting and clarification process of the glass. The mixed alkali effect of K2O and Na2O can reduce the surface tension of the glass. At the same time, K2O and / or Na2O can also play a role in fluxing, accelerating the melting and clarification process of the glass. + and / or Na +The incorporation of these two ions helps optimize the glass structure, thereby enhancing its mechanical properties. A balanced ratio of K2O and / or Na2O is crucial for maintaining the chemical stability and mechanical strength of the glass. Excessive K2O and / or Na2O content can reduce the chemical stability and mechanical strength of the glass, while insufficient K2O and / or Na2O content can fail to effectively lower the melting point and improve processability. In some embodiments of the present invention, the content of K2O is further 9-13.5%, preferably 9.6-13.5%, more preferably 9.6-12%, and the content of K2O can 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 NaO2 is further 0%, preferably 9.6-13.5%, more preferably 9.6-12%, and the content of K2O can 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%. -15% or 10-20%, preferably 0-12%, more preferably 10-12% or 0; and, the content of NaO2 can 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 aforementioned K2O and / or Na2O content ranges, particularly within the preferred ranges, the glass material is further guaranteed to achieve a suitable melting point, good processability, mechanical properties, and chemical stability. In particular, in some embodiments of the present invention, when the K2O content is not less than 0.8 times the Na2O content, the synergistic effect of SiO2 and B2O3 is further promoted, and the chemical stability and mechanical strength of the glass material are better balanced.

[0012] In an embodiment of the present invention, BaO with a mass percentage of 0.1-1% is further introduced into the glass material. The introduction of BaO at this content can provide free oxygen, promote the melting of glass, and improve the drawing of glass fibers. At the same time, the introduction of BaO at this content can also help slow down the speed of radiated ions, and has the ability to capture rays, which can reduce the probability of glass structure being destroyed and enhance the radiation resistance of the glass material. However, it should be noted that the introduction of BaO will bring better radiation resistance, but it will also affect the chemical stability of the glass material. In particular, when the content is too high, it will significantly reduce the chemical stability of the glass material, while a lower content will make the radiation resistance insufficient, and an even lower content will make the radiation resistance insufficient. On this basis, CeO2 with a mass percentage of 2-5% is also introduced into the glass material described in the present invention. This content of CeO2 can effectively inhibit the generation of color centers in a radiation environment, improve radiation stability, and have good ultraviolet absorption capacity. At the same time, it also helps to clarify and reduce the generation of glass defects. It can also play a synergistic and complementary role with 0.1-1% BaO, helping to improve transmittance and enhance radiation resistance, achieving a good balance between transmittance and radiation resistance, while avoiding the adverse effects of the introduction of BaO on chemical stability. However, it should be noted that CeO2 cannot be too high. For example, when it is higher than 1%, it will significantly reduce the transmittance of the glass material. In an embodiment of the present invention, a series of suitable BaO and CeO2 contents are provided. For example, in some embodiments of the present invention, the BaO content is 0.2-1%, preferably 0.3-1%, more preferably 0.1-0.4%, further preferably 0.1-0.3% or 0.3-0.4%, and the BaO content can also be selected from the following: 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 CeO2 is 2.5-5%, preferably 2.5-4% or 4-5%, and the content of CeO2 can also be selected from the following: 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%. Within the above-mentioned content ranges of BaO and CeO2, especially within the preferred content ranges, the radiation resistance and transmittance of the glass material can be well balanced, and the chemical properties of the material can be further stabilized. In particular, in some embodiments of the present invention, the content of CeO2 should be no less than 2.7 times the content of BaO, which can better exert the synergistic and complementary effects of CeO2 and BaO.

[0013] In embodiments of the present invention, Al2O3 and MgO are also introduced. These structure-modifying oxides work together to reduce the glass's crystallization tendency and thermal expansion coefficient, thereby improving thermal stability. Furthermore, their introduction also enhances the glass's chemical stability and mechanical strength. However, it should be noted that the Al2O3 and MgO content must be controlled to avoid negative impacts on glass fluidity and other factors, and to reduce manufacturing costs. For example, excessive Al2O3 content increases the viscosity of the molten glass, making melting and clarification difficult and, in turn, increasing the tendency to crystallize. Similarly, excessive MgO content negatively impacts glass properties, increases the tendency to crystallize, and increases annealing temperatures, increasing manufacturing costs. Therefore, in embodiments of the present invention, the Al2O3 content is controlled to be 1-2% by weight, and the MgO content is controlled to be 2.7-5% by weight. Furthermore, a range of suitable Al2O3 and MgO content is provided in embodiments of the present invention. For example, in some embodiments of the present invention, the content of Al2O3 is 1-1.5%, preferably 1-1.4%, more preferably 1-1.1% and or 1.4-1.5%, calculated by mass percentage; and the content of Al2O3 can 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 present invention, the MgO content is 2.7-4%, preferably 2.7-3.9%, more preferably 2.7-3.4% or 3.4-5%, by weight. Furthermore, the MgO content may 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%, and 3.9-4%. In particular, in some embodiments of the present invention, the CeO content should be no less than 2.7 times the BaO content. This allows for better synergistic effects between Al2O3 and MgO.

[0014] In some embodiments of the present invention, the glass material described in the present invention is composed of the following components, calculated by mass percentage: SiO2 45-60%; BaO 0.1-1%; B2O3 10-18%; CeO2 2-5%; Al2O3 1-1.5%; MgO 2.7-5%; NaO2 0-20%; K2O 9%-13.1%, and the sum of the mass percentages of each component is 100%.

[0015] In some embodiments of the present invention, the glass material described in the present invention is composed of the following components, calculated by mass percentage: SiO2 45-60%; BaO 0.3-1%; B2O3 10-17%; CeO2 2.1-5%; Al2O3 1-1.5%; MgO 2.7-5%; NaO2 0-12%; K2O 9%-13.1%, and the sum of the mass percentages of each component is 100%.

[0016] In some embodiments of the present invention, the glass material described in the present invention is composed of the following components, calculated by mass percentage: SiO2 45-60%; BaO 0.3-1%; B2O3 10-17%; CeO2 2.7-5%; Al2O3 1-1.4%; MgO 2.7-3.4%; NaO2 10-12%; K2O 9.6%-11%, and the sum of the mass percentages of each component is 100%.

[0017] In some embodiments of the present invention, the glass material described in the present invention is composed of the following components, calculated by mass percentage: SiO2 59-60%; BaO 0.3-1%; B2O3 10-17%; CeO2 2.7-5%; Al2O3 1-1.4%; MgO 2.7-3.4%; NaO2 10-12%; K2O 9.6%-11%, and the sum of the mass percentages of each component is 100%.

[0018] The present invention produces glass with uniform internal quality, stable composition, and good mechanical stability by adjusting the contents of SiO2, B2O3, Na2O, and K2O. Furthermore, by controlling the transmittance and radiation resistance of the glass, BaO, CeO2, and other elements are controlled to balance the transmittance and radiation resistance of the glass, resulting in excellent overall shielding performance against α and β rays and resistance to gamma radiation, while also exhibiting good optical transmittance. Furthermore, by introducing and controlling the contents of Al2O3 and MgO, the glass's crystallization tendency and thermal expansion coefficient are reduced, improving thermal stability while further enhancing the glass's chemical stability and mechanical strength. The combination of these components also reduces the viscosity of the molten glass, easing the difficulty of glass molding, and lowering the surface tension of the glass, improving the glass's mechanical properties and sealing properties, making it easier to process and manufacture. The resulting glass material not only exhibits excellent shielding performance against α and β rays and resistance to gamma radiation, but also maintains excellent transmittance, chemical stability, and mechanical properties, particularly after repeated high-dose gamma ray irradiation. It is easy to process and manufacture, making it more suitable for practical applications.

[0019] 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 in proportion, melting at high temperature, stirring, and then clarifying at high temperature and forming to obtain the glass material.

[0020] In one embodiment of the present invention, the method comprises:

[0021] S1. Mix glass components including quartz sand, boric acid, alkali metal and / or alkaline earth metal salts in proportion, then add clarifier in proportion and mix well;

[0022] S2, melting the mixture at high temperature and stirring;

[0023] S3. Clarifying and forming the mixture through high-temperature stirring to obtain a glass material.

[0024] In some embodiments of the present invention, the alkali metal and / or alkaline earth metal salts are carbonates and / or nitrates.

[0025] In some embodiments of the present invention, the high temperature melting temperature is 1360-1450° C., and the melting time is 9-30 hours.

[0026] In some embodiments of the present invention, the stirring speed is 10-40 r / min and the stirring time is 10-14 hours. Before glass forming, there are certain requirements for the uniformity of the feed liquid. Therefore, it is necessary to stir the glass liquid at a certain speed for a period of time to improve the uniformity and clarity of the feed liquid. If the feed liquid has low uniformity, the feed liquid is prone to stratification or agglomeration, making it difficult to melt, clarify, and homogenize the glass. In severe cases, it may even produce streaks or stone defects. Low feed liquid clarity can cause bubbles in the formed glass, reducing the quality of the glass.

[0027] In some embodiments of the present invention, the molding temperature is 1060-1150° C. and the molding time is 5-25 minutes. The rapid molding of glass prevents the generation of secondary bubbles and impurities.

[0028] In a third 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;

[0029] In some embodiments of the present invention, the optical element can shield gamma rays, alpha rays, and beta rays.

[0030] In a fourth aspect of the present invention, there is provided a radiation shielding material comprising the glass material described in the first aspect or made of the glass material described in the first aspect;

[0031] In some embodiments of the present invention, the radiation shielding material is used to shield gamma rays, alpha rays, and beta rays;

[0032] In some embodiments of the present invention, the radiation shielding material is a radiation shielding window material.

[0033] In a fourth aspect of the present invention, there is provided an application of the glass material described in the first aspect, the optical element described in the third aspect, or the radiation shielding material described in the fourth aspect in the optical field or the radiation shielding field.

[0034] In some embodiments of the present invention, the radiation shielding field or the optical field is selected from the nuclear industry field, the nuclear medicine field and the space exploration field.

[0035] In some embodiments of the present invention, the application is use as a radiation shielding window material.

[0036] 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.

[0037] Unless otherwise specified, the numerical ranges described in the present invention include all values ​​within the range, and include the range values ​​formed by any two values ​​within the range. For example, the numerical range of 0.3-1% includes all values ​​between 0.3-1%, and includes the range value (0.31-0.99%) formed by any two values ​​within the range (for example, 0.31% and 0.99%). Different numerical values ​​of the same indicator appearing in all embodiments of the present invention can be arbitrarily combined to form a range value.

[0038] By using one or more of the above technical means, the following beneficial effects can be achieved:

[0039] The glass material provided by the present invention has the following characteristics: high transmittance, high chemical stability, good shielding performance against α-rays and β-rays, ability to withstand high-energy ray irradiation, and good mechanical properties. Before irradiation, the glass material provided by the present invention has a maximum transmittance of ≥90.3% and a minimum transmittance of ≥70.1% within the range of 400-800nm. 6 After irradiation with a high dose of 10 Gy gamma rays, the maximum transmittance is ≥88.1% and the minimum transmittance is ≥53.8% in the range of 400-800 nm. The transmittance and mechanical strength of the glass of the present invention change very little before and after irradiation, and the chemical stability hardly changes, indicating that it has good radiation resistance. In particular, the glass of the present invention can still have good transmittance, chemical stability and mechanical strength after multiple irradiations. For example, in an embodiment of the present invention, after 3 1×10 6After irradiation with a high dose of gamma rays, the transmittance of the glass of the present invention in the range of 400-800 nm is still higher than 87%.

[0040] The present invention provides a glass material with a suitable melting temperature (1360-1450° C.), good anti-devitrification performance, good mechanical properties, easy molding and convenient processing and manufacturing.

[0041] Existing glass has low transmittance over a wide wavelength range. Furthermore, after irradiation with high-intensity, high-energy radiation, the glass material is prone to developing color centers, which affects its transmittance. This invention, by selecting and adjusting the comprehensive ratio of components such as BaO, CeO2, Al2O3, and MgO, produces a high-transmittance, highly chemically stable, radiation-resistant glass. This glass maintains a high transmittance even after multiple high-dose gamma ray irradiations. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] 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:

[0043] Figure 1 is a schematic diagram of an optical glass turbidity measurement device used to test the moisture resistance stability of glass, where: 1 is the light source; 2 is the collimator; 3 is the sample; 4 is the integrating sphere; 5 is the photodetector; 6 is the light trap; and 7 is the standard white plate.

[0044] FIG2 is a glass product of the present invention and a comparative glass product through 1×10 6 Gy gamma ray irradiation before and after the transmittance comparison curve in the range of 400-800nm.

[0045] FIG3 shows a glass product of the present invention and a comparative glass product after irradiation with gamma rays for three times (the irradiation dose for each time is 1×10 6 Gy), comparison of the maximum transmittance in the range of 400-800 nm before and after each irradiation. DETAILED DESCRIPTION

[0046] 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.

[0047] 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. If not 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 method and material similar to or equivalent to the described content can be applied to the method of this application. The preferred implementation methods and materials described in the article are for demonstration purposes only. In the present invention, weight percentage (weight percentage) and mass percentage (mass percentage) have the same meaning, indicating the proportion of a certain component in a mixture. This proportion is calculated by dividing the mass of the component by the total mass of the entire mixture and then multiplying by 100%, and is expressed in wt%.

[0048] The performance parameters in the following examples were measured using the following methods:

[0049] The thermal expansion coefficient of glass samples was measured using a DIL 402 expansion coefficient tester manufactured by NETZSCH, Germany. Sample preparation: The glass samples were ground and polished into cylindrical glass strips measuring Φ6 x 50 mm, with the two ends parallel. The heating rate was set at 5°C / min, and the data acquisition cycle was 20ms. The data were plotted against the temperature and linear expansion curves, and the glass transition temperature and dilatometric softening temperature were obtained using the tangent method. (GB / T 7962.16-2010)

[0050] The transmittance was tested using a UV-visible-infrared spectrophotometer.

[0051] Acid Stability Test: Solutions with pH values ​​of 2.9, 4.6, and 6.0 are used as the test medium. After the polished glass sample surface is corroded by the test medium, the time it takes for the glass surface to develop a purplish-blue interference color, or for the surface to exhibit mottled or flaky colors, is observed under an incandescent lamp. The acid stability of colorless optical glass is then classified in descending order based on the time it takes. (GB / T 7962.14-2010)

[0052] Glass Moisture Stability Test: Use the device shown in Figure 1 to measure the turbidity H0 and H1 of the test sample and standard samples (BaK7 glass and ZK9 glass) before and after erosion. Calculate the turbidity value H by H = H1 - H0. Compare it with the turbidity value of the standard sample and refer to the table to determine the moisture stability grade of the optical glass. (GB / T 7962.15-2010)

[0053] Glass bending strength test: By measuring the width b of the middle part of the sample, the thickness d, the distance L between the two sample supports, and the maximum load P when the sample breaks, the bending strength of the sample is obtained by substituting into the following formula (GB / T 37781~2019):

[0054] Among them, σ b is the bending strength of the specimen, in megapascals (MPa); P is the maximum load when the specimen breaks, in Newtons (N); b is the width of the specimen, in millimeters (mm); and d is the thickness of the specimen, in millimeters (mm).

[0055] Glass hardness test: Use a square pyramid diamond indenter with symmetrical angles of 172°30' and 130°, apply a certain load to it and press it vertically on the sample surface. After maintaining it for a certain period of time, remove the load, observe and measure the length of the long diagonal of the indentation on the sample with a microscope, convert the projected area of ​​the indentation, and substitute it into the following formula to calculate the Kirkmarsh hardness H K (GB / T 7962.18~2010):

[0056] Where, F is the applied load, in Newton (N); d is the length of the diagonal of the indentation, in millimeters (mm); H K Kerr hardness, unit is 10 7 Pascal (10 7 Pa).

[0057] The present invention will be further described below with reference to specific embodiments.

[0058] Example 1

[0059] The components of the glass material of this embodiment and the weight percentage of each component are shown in Table 1, and the physical properties are shown in Table 2.

[0060] The preparation method is as follows: quartz sand, boric acid, aluminum hydroxide, potassium carbonate, sodium carbonate, barium oxide, aluminum oxide and magnesium oxide are used as raw materials, a clarifier CeO2 is added, and the weight of the clarifier accounts for 5.0% of the weight of the glass. After sufficient mixing, the raw materials are melted at a high temperature of 1360°C for 9 hours, mechanically stirred (10 r / min, 10 hours), assisted by high-temperature clarification, and molded by pouring or casting at 1060°C (molding time is 5 minutes) to obtain a glass blank.

[0061] Example 2

[0062] The components of the glass material of this embodiment and the weight percentage of each component are shown in Table 1, and the physical properties are shown in Table 2.

[0063] In the preparation method, the clarifier is CeO2, and the weight of the clarifier accounts for 3.0% of the weight of the glass; the melting temperature is 1400°C, and the melting time is 17 hours; mechanical stirring is used (25 r / min, 13 hours), the molding temperature is 1100°C, and the molding time is 15 minutes. The other preparation steps and parameters are the same as those in Example 1.

[0064] Example 3

[0065] The components of the glass material of this embodiment and the weight percentage of each component are shown in Table 1, and the physical properties are shown in Table 2.

[0066] In the preparation method, the clarifier is CeO2, and the weight of the clarifier accounts for 2.3% of the weight of the glass; the melting temperature is 1450°C, and the melting time is 30 hours; mechanical stirring is performed (40 r / min, 14 hours), the molding temperature is 1150°C, and the molding time is 25 minutes. The other preparation steps and parameters are the same as those in Example 1.

[0067] Example 4

[0068] The components of the glass material of this embodiment and the weight percentage of each component are shown in Table 1, and the physical properties are shown in Table 2.

[0069] In the preparation method, the clarifier is CeO2, and the weight of the clarifier accounts for 2.0% of the weight of the glass; the melting temperature is 1390°C, and the melting time is 20 hours; mechanical stirring is performed (20 r / min, 12 hours), the molding temperature is 1080°C, and the molding time is 15 minutes. The other preparation steps and parameters are the same as those in Example 1.

[0070] Example 5

[0071] The components of the glass material of this embodiment and the weight percentage of each component are shown in Table 1, and the physical properties are shown in Table 2.

[0072] In the preparation method, the clarifier is CeO2, and the weight of the clarifier accounts for 2.1% of the weight of the glass; the melting temperature is 1420°C, and the melting time is 25 hours; mechanical stirring is performed (35 r / min, 14 hours), the molding temperature is 1100°C, and the molding time is 25 minutes. The other preparation steps and parameters are the same as those in Example 1.

[0073] Example 6

[0074] The components of the glass material of this embodiment and the weight percentage of each component are shown in Table 1, and the physical properties are shown in Table 2.

[0075] In the preparation method, the clarifier is CeO2, and the weight of the clarifier accounts for 3.0% of the weight of the glass; the melting temperature is 1410°C, and the melting time is 17 hours; mechanical stirring is performed (25 r / min, 13 hours), the molding temperature is 1100°C, and the molding time is 20 minutes. The other preparation steps and parameters are the same as those in Example 1.

[0076] Example 7

[0077] The components and weight percentages of the glass material of this embodiment are shown in Table 1, and the physical properties are shown in Table 2. The preparation method is the same as that of Example 1.

[0078] Example 8

[0079] The components and weight percentages of the glass material of this embodiment are shown in Table 1, and the physical properties are shown in Table 2. The preparation method is the same as that of Example 1.

[0080] Example 9

[0081] The components and weight percentages of the glass material of this embodiment are shown in Table 1, and the physical properties are shown in Table 2. The clarifier in the preparation method is CeO2, and the weight of the clarifier accounts for 2.6% of the weight of the glass. The other preparation steps and parameters are the same as in Example 1.

[0082] Comparative Examples 1-8

[0083] The components of the glasses of Comparative Examples 1-8 and the weight percentages of the components are shown in Table 3, and the physical properties are shown in Table 4.

[0084] The preparation steps and parameters of the glass in Comparative Examples 1-8 are the same as those in Example 1.

[0085] Table 1 Components and contents of the glass materials described in Examples 1-9 of the present invention

[0086] Table 2 Physical properties of the glass materials described in Examples 1-9 of the present invention

[0087] Table 3 Components and contents of the glass materials described in Comparative Examples 1-8

[0088] Table 4 Physical properties of the glass materials described in Comparative Examples 1-8

[0089] Ts in Table 2 and Table 4 is the softening point, that is, the point at which the glass viscosity reaches 10 7.6 dPa·s temperature; α 30-300℃ is the thermal expansion coefficient of glass measured in the range of 30-300°C; the irradiation is performed with an irradiation dose of 1×10 6 Gy of gamma ray irradiation.

[0090] By rationally adding corresponding components and adjusting the ratio of each component in the raw materials, the optical transmittance and radiation resistance of the glass obtained in Examples 1-9 of the present invention are better. As can be seen from Table 2, the optical transmittance of the glass obtained in Examples 1-9 of the present invention is as follows: before irradiation, the maximum transmittance in the range of 400-800nm ​​is ≥90.2%, and the minimum transmittance is ≥70.1%. 6After a single irradiation of 100 Gy, the maximum transmittance within the 400-800 nm range is ≥84.4%, and the minimum transmittance is ≥53.2%. In particular, the glass of the present invention maintains excellent transmittance, chemical stability, and mechanical properties even after multiple irradiations. For example, after three irradiations of gamma rays, the maximum transmittance within the 400-800 nm range of the glass of Example 1 remains above 87% (see Figures 1 and 2). The glasses produced in Examples 1-9 exhibit superior transmittance, chemical stability, and radiation resistance to the glasses described in the comparative examples. Furthermore, they possess excellent mechanical properties and are easy to process and manufacture.

[0091] As can be seen from the foregoing, the high-transmittance, high-chemical stability, high-energy radiation-resistant glass provided in Examples 1-9 of the present invention exhibits excellent optical transmittance, chemical stability, and good radiation resistance. The specific technical features described in the above embodiments of the present invention may be combined in any suitable manner, unless they conflict with each other. To avoid unnecessary repetition, the present invention will not further describe the various possible combinations.

[0092] The glass material of the present invention has high optical transmittance, good chemical stability and excellent radiation resistance, good processing performance and sealing performance, and good comprehensive performance. It can be used as the main material for radiation shielding windows and can also be used in other high-energy radiation environments such as aviation, aerospace, and medicine, and has broad application prospects.

[0093] 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, by mass percentage, comprises or consists of the following components: SiO2 45 - 60%; BaO 0.1 - 1%; B2O3 10 - 20%; CeO2 2 - 5%; Al2O3 1 - 2%; MgO 2.7 - 5%; NaO2 0 - 20%; K2O 9% - 15%.

2. The glass material according to claim 1, wherein By mass percentage, the content of SiO2 is 50 - 60%, preferably 56 - 60%, more preferably 59 - 60%; Preferably, by mass percentage, the content of BaO is 0.2 - 1%, preferably 0.3 - 1%, more preferably 0.1 - 0.4%, even more preferably 0.1 - 0.3% or 0.3 - 0.4%; Preferably, by mass percentage, the content of B2O3 is 10 - 18%, preferably 10 - 17%; Preferably, by mass percentage, the content of CeO2 is 2.5 - 5%, preferably 2.5 - 4% or 4 - 5%; Preferably, by mass percentage, the content of Al2O3 is 1 - 1.5%, preferably 1 - 1.4%, more preferably 1 - 1.1% and / or 1.4 - 1.5%; Preferably, by mass percentage, the content of MgO is 2.7 - 4%, preferably 2.7 - 3.9%, more preferably 2.7 - 3.4%; Preferably, by mass percentage, the content of NaO2 is 0 - 15% or 10 - 20%, preferably 0 - 12%, more preferably 10 - 12% or 0; Preferably, by mass percentage, the content of K2O is 9 - 13.5%, preferably 9.6 - 13.5%, more preferably 9.6 - 12%.

3. The glass material according to claim 1 or 2, wherein By mass percentage, it consists of the following components: SiO2 45 - 60%; BaO 0.1 - 1%; B2O3 10 - 18%; CeO2 2 - 5%; Al2O3 1 - 1.5%; MgO 2.7 - 5%; NaO2 0 - 20%; K2O 9% - 13.1%, and the sum of the mass percentages of each component is 100%; Preferably, by mass percentage, it consists of the following components: SiO2 45 - 60%; BaO 0.3 - 1%; B2O3 10 - 17%; CeO2 2.1 - 5%; Al2O3 1 - 1.5%; MgO 2.7 - 5%; NaO2 0 - 12%; K2O 9% - 13.1%, and the sum of the mass percentages of each component is 100%; Preferably, by mass percentage, it consists of the following components: SiO2 45 - 60%; BaO 0.3 - 1%; B2O3 10 - 17%; CeO2 2.7 - 5%; Al2O3 1 - 1.4%; MgO 2.7 - 3.4%; NaO2 10 - 12%; K2O 9.6% - 11%, and the sum of the mass percentages of each component is 100%; Preferably, it consists of the following components by mass percentage: SiO2 59 - 60%; BaO 0.3 - 1%; B2O3 10 - 17%; CeO2 2.7 - 5%; Al2O3 1 - 1.4%; MgO 2.7 - 3.4%; NaO2 10 - 12%; K2O 9.6% - 11%, and the sum of the mass percentages of each component is 100%.

4. The glass material according to any one of claims 1 to 3, wherein The content of SiO2 is not less than 2.6 times the content of B2O3; Preferably, the content of K2O is not less than 0.8 times the content of Na2O; Preferably, the content of CeO2 is not less than 2.7 times the content of BaO.

5. A method for preparing the glass material according to any one of claims 1 to 4, comprising: Mix the raw materials in proportion, melt them at high temperature, stir, and then clarify and shape them at high temperature to obtain the glass material.

6. The method according to claim 5, wherein The method includes: Mix the glass components, including quartz sand, boric acid, alkali metal and / or alkaline earth metal salts in proportion, and then add a clarifying agent in proportion and mix well; Melt the mixture at high temperature and stir; Obtain the glass material through stirring clarification and shaping.

7. The method according to claim 5 or 6, wherein The alkali metal and / or alkaline earth metal salts are carbonates and / or nitrates; Preferably, the temperature for high-temperature melting is 1360 - 1450 °C, and the melting time is 9 - 30 h; Preferably, the stirring speed is 10 - 40 r / min, and the stirring time is 10 - 14 h; Preferably, the shaping temperature is 1060 - 1150 °C, and the shaping time is 5 - 25 min.

8. An optical element, which comprises the glass material according to any one of claims 1 to 4 or is made of the glass material according to any one of claims 1 to 4; Preferably, the optical element can shield gamma rays, alpha rays and beta rays.

9. A radiation shielding material, which comprises the glass material according to any one of claims 1 to 4 or is made of the glass material according to any one of claims 1 to 4; Preferably, the radiation shielding material is used to shield gamma rays, alpha rays and beta rays; Preferably, the radiation shielding material is a radiation shielding window material.

10. Use of the glass material according to any one of claims 1 to 4, or the optical element according to claim 8, or the radiation shielding material according to claim 9, in the field of optics or radiation shielding; Preferably, the use is as a radiation shielding window material; Preferably, the radiation shielding field or the optical field is selected from the fields of nuclear industry, nuclear medicine and space exploration.

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