High-transmittance neutron-gamma composite shielding glass as well as preparation method and application thereof

Abstract

The invention relates to the field of special glass materials, in particular to high-transmittance neutron-gamma composite shielding glass as well as a preparation method and application thereof. Wherein the glass comprises the following components in percentage by mass: 2%-7% of SiO2; 16% to 25% of B2O3; 1% to 5% of Al2O3; 10%-20% of BaO; 0 to 5% of Bi2O3; 6%-10% of SrO; 36% to 41% of La2O3; 0.5% to 4% of Y2O3; 1%-8% of Li2O; 10% to 15% of Nb2O5; 0 to 5% of ZrO2; 0.01% to 0.1% of CeO2; and 0.2%-0.4% of Sb2O3. The glass keeps high optical transmittance, also provides excellent gamma ray and fast neutron protection capability, has good chemical stability and high temperature resistance, can realize large-size production, and is suitable for the fields needing integrated composite radiation shielding in extremely complex radiation environments such as medical treatment, industry and research.

Description

Technical Field

[0001] The present invention relates to the field of special glass materials, and particularly to a high transmittance neutron gamma composite shielding glass, its preparation method and application. Background Art

[0002] Any discussion of the prior art throughout the specification should not be taken as an admission that such prior art is well known or forms part of the common general knowledge in the art.

[0003] With the rapid development of the nuclear technology application industry, various rays are widely used in fields such as medical treatment, aviation, national defense, and nuclear industry. People's demand for radiation protection is increasing day by day. To ensure public health and safety, radiation shielding technology must be continuously improved and enhanced. The basic requirement of nuclear radiation protection is to have good shielding performance against γ-rays and neutrons (especially fast neutrons above 1 MeV).

[0004] In many application scenarios, transparent radiation protection materials have unique advantages. They not only meet the needs of human eye observation but also can effectively avoid the damage of ionizing radiation to the human body. Glass materials, with their high transparency, recyclability, light weight, chemical resistance, reasonable price, easy processing, and harmlessness to the human body, have become an ideal choice in the field of radiation shielding.

[0005] Traditional radiation shielding materials include lead, tungsten, concrete, and polymer-based composites, etc. Although they have good shielding performance, they lack transparency and some have environmental pollution problems. Existing research shows that the shielding effect of materials on gamma rays is closely related to their effective atomic number, while neutron shielding includes two processes: fast neutron moderation and thermal neutron absorption. To achieve effective shielding, researchers usually add high atomic number element oxides (such as PbO) to the glass to shield gamma rays, and add high thermal neutron capture cross-section oxides (such as B2O3, Gd2O3, Sm2O3, and Eu2O3, etc.) to absorb thermal neutrons.

[0006] However, existing neutron gamma composite shielding glasses are difficult to be applied on a large scale and face two major challenges: on the one hand, hydrogen element, which can effectively moderate fast neutrons, is difficult to be incorporated into the inorganic glass network. Although hydrogen-containing organic materials have good neutron moderation effect, their structural stability is poor and they are easy to form color centers. Other known elements (such as transition metals like osmium, iridium, gold, platinum, etc.) with relatively high fast neutron removal cross-section (FNRCS) are rare and expensive and difficult to be doped in large quantities; on the other hand, high atomic number oxides such as PbO not only have environmental pollution problems but also significantly reduce the glass transmittance, increase the expansion coefficient, lower the softening point, and weaken the chemical stability, affecting the long-term use performance. Although the current technology has made some progress in certain single aspects, it has not been able to simultaneously solve the comprehensive challenges in multiple aspects such as transmittance, shielding performance, and stability.

[0007] At present, neutron-gamma composite shielding glass with good performance in terms of transmittance, shielding performance, stability, etc. remains an important research direction in the industry. Summary of the Invention

[0008] The object of the present invention is to provide a high-transmittance neutron-gamma composite shielding glass and its preparation method and application, aiming to solve one or more problems existing in the prior art, including low transmittance, insufficient shielding performance, poor stability, etc.

[0009] Specifically, the technical problem to be solved by the present invention is: how to optimize the component ratio and / or preparation process so that the glass material can achieve one or more of the following technical characteristics: improved optical transmittance performance, maintaining a high transmittance in the visible light wavelength range of 350 - 900 nm; enhanced gamma-ray shielding performance, avoiding or reducing the use of components such as PbO that are harmful to the use environment; enhanced fast neutron shielding ability, improving the problem of insufficient fast neutron shielding efficiency of existing glass; improved high-temperature stability, including an appropriate coefficient of thermal expansion, a higher glass transition temperature and sag temperature; improved chemical stability and mechanical strength, which is beneficial for long-term use; suitable for industrial production and processing, facilitating practical application.

[0010] In the optimal state, the high-transmittance neutron-gamma composite shielding glass provided by the present invention can simultaneously possess all or most of the above technical characteristics, thus providing a comprehensive solution for nuclear radiation protection in different application scenarios.

[0011] The present invention realizes the above technical objectives by carefully selecting and adjusting the types and ratios of raw materials, especially the ratio relationship of rare earth elements and transition metal oxides, and the reasonable use of clarifying agents, providing a new shielding material with advanced technology, stable performance and environmental friendliness in the field of nuclear radiation protection.

[0012] Specifically, the present invention provides the following technical solutions.

[0013] In the first aspect of the present invention, there is provided a high-transmittance neutron-gamma composite shielding glass, which comprises the following components in mass percentage or consists of the following components in mass percentage (mass%):

[0014] SiO2 2% - 7%; B2O3 16% - 25%; Al2O3 1% - 5%; BaO 10% - 20%; Bi2O3 0 - 5%; SrO 6% - 10%; La2O3 36% - 41%; Y2O3 0.5% - 4%; Li2O 1% - 8%; Nb2O5 10% - 15%; ZrO2 0 - 5%; CeO2 0.01% - 0.1%; Sb2O3 0.2% - 0.4%.

[0015] In the present invention, the contents of all components are expressed in mass percentages, that is, each component is calculated in the form of its oxide and represents the percentage of the total mass of the glass. Specifically, regardless of whether the raw materials are added in the form of oxides, carbonates, nitrates, halides or other compounds, their contents are calculated based on the oxides formed in the final glass. This calculation method is based on the assumption that during the glass melting process, all raw materials are finally converted into the corresponding oxide forms, and the sum of these oxides is set to 100%, and the content of each component is the proportion it occupies in this total amount. Unless otherwise specified, all component contents mentioned in the present invention are calculated using this conversion method.

[0016] SiO2 is the main glass-forming oxide, forming a silicon-oxygen tetrahedron structure network that constitutes the framework of the glass, and its structural state in the glass plays a decisive role in the glass properties. In the present invention, the content of SiO2 does not exceed 7%. If its content is too high, it will reduce the thermal expansion coefficient of the glass, improve the thermal stability, chemical stability, softening temperature and mechanical strength of the glass, but it will also cause an increase in the melting point and an increase in the melting difficulty.

[0017] Therefore, in the present invention, the content range of SiO2 is 2% - 7%. Among them, the lower limit of the content of SiO2 is preferably 2%, more preferably 3%, still more preferably 4% or 5%, and most preferably 6%; the upper limit is preferably 7%, more preferably 6%. In the more preferred range, the content of SiO2 is 2% - 7% or 2% - 6%, more preferably 3% - 7% or 3% - 6%, still more preferably 4% - 7% or 4% - 6%, and most preferably 5% - 7% or 5% - 6% or 6% - 7%. In particular, in some embodiments of the present invention, the content of SiO2 can be any value among 2%, 2.5%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.75%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9% or 7%, or any range composed of any two of these values, or any value within this range.

[0018] In the high-transmittance neutron-gamma composite shielding glass of the present invention, B2O3, as a key functional component, through its specific content range (16% - 25%) and the synergistic effect with other components, achieves multiple technical effects. B2O3 takes borate triangles [BO3] and borate tetrahedrons [BO4] as structural units, and together with the silicon-oxygen tetrahedrons formed by SiO2 in the formulation system of the present invention, constructs the glass network structure, significantly affecting the physical and chemical properties of the glass.

[0019] In the present invention, by controlling the B2O3 content within the range of 16% - 25%, the following technical effects are achieved: (1) effectively reducing the thermal expansion coefficient of the glass to the ideal range of (70 - 80)×10 -7 / ℃; (2) cooperating with La2O3, enabling the glass transition temperature Tg and the sag temperature Ts of the glass to reach above 600℃ and 650℃ respectively; (3) synergistically with the Li2O component, the high absorption capacity for thermal neutrons constructs a dual protection mechanism for thermal neutron absorption and fast neutron moderation, making the neutron shielding rate reach more than 50%; (4) fully exerting the fluxing effect at the melting temperature of 1200 - 1350℃ to ensure the uniformity and high transmittance of the glass.

[0020] However, when the addition amount of B2O3 exceeds 25%, due to the excessive increase of boron - oxygen triangles, it will cause the boron anomaly in the glass, increasing the thermal expansion coefficient and decreasing the shielding performance and transmittance. Therefore, the upper limit of the present invention is strictly controlled at 25%. Through experiments, it is found that when the B2O3 content is 16% - 20%, better comprehensive performance is exhibited. Among them, within the range of 16% - 18%, the shielding effect and light transmittance are best balanced. Especially within the range of 16% - 17%, such as the 17% content in Example 3, the glass shows better neutron shielding rate (52.4%) and gamma - ray shielding rate (53.4%).

[0021] In a more preferred embodiment of the present invention, the content of B2O3 can be 16% - 20%, preferably 16% - 19%, more preferably 16% - 18%, and most preferably 16% - 17%. In particular, in some embodiments of the present invention, the content of B2O3 can be any value among 16%, 16.1%, 16.2%, 16.3%, 16.4%, 16.5%, 16.6%, 16.7%, 16.8%, 16.9%, 17%, 17.1%, 17.2%, 17.3%, 17.4%, 17.5%, 17.6%, 17.7%, 17.8%, 17.9%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5% or 25%, or any range composed of any two of these values, or any value within this range.

[0022] Al2O3 belongs to glass intermediate oxides. In the present invention, 1%-5% of Al2O3 can reduce the crystallization tendency of the glass, improve the viscosity, chemical stability, thermal stability and mechanical strength of the glass, reduce the erosion of the glass on refractory materials. In the preferred range of the present invention, the content of Al2O3 can be 1%-5%, preferably 1%-3%, more preferably 2%-3%. In particular, in some embodiments of the present invention, the content of Al2O3 can be any value among 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.5%, 3.6%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5%, or any range composed of any two of these values, or any value within this range.

[0023] BaO is an external glass network oxide. In the present invention, 10%-20% of BaO can increase the refractive index, density, gloss and chemical stability of the glass, and accelerate the melting of the glass. Particularly importantly, BaO within this content range can improve the gamma-ray absorption capacity of the glass, which is beneficial for gamma-ray shielding. In the preferred range of the present invention, the content of BaO is 10%-20%, preferably 11%-20%, more preferably 10%-15%, and more preferably 11%-12%. In particular, in some embodiments of the present invention, the content of BaO can be any value among 10%, 10.1%, 10.2%, 10.3%, 10.4%, 10.5%, 10.6%, 10.7%, 10.8%, 10.9%, 11%, 11.1%, 11.2%, 11.3%, 11.4%, 11.5%, 11.6%, 11.7%, 11.8%, 11.9%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5% or 20%, or any range composed of any two of these values, or any value within this range.

[0024] Bi2O3 is an external oxide of the glass network. In the present invention, Bi2O3 with a content of no more than 5% can significantly reduce the viscosity of the glass, increase the density of the glass, and improve the gamma-ray shielding ability. However, if the content of Bi2O3 is too high, such as higher than 5%, it will cause a serious decrease in the transmittance of the glass. Therefore, the content needs to be strictly controlled. In the preferred range of the present invention, the content of Bi2O3 is 0 - 5%, preferably 0.1 - 5%, more preferably 0.5% - 5%, and most preferably 1% - 5%. In particular, in some embodiments of the present invention, the content of Bi2O3 can be any value among 0, 0.1%, 0.5%, 1%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5%, or any range composed of any two of these values, or any value within this range.

[0025] SrO is an external oxide of the glass network, and its function is between that of CaO and BaO. In the present invention, SrO and BaO cooperate to provide gamma-ray shielding ability and improve the chemical stability of the glass at the same time. In the preferred range of the present invention, the content of SrO can be 6% - 10%, preferably 7% - 10% or 6% - 8% or 7% - 8%. In particular, in some embodiments of the present invention, the content of SrO can be any value among 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8%, 8.5%, 9%, 9.5% or 10%, or any range composed of any two of these values, or any value within this range.

[0026] La2O3 is an external oxide of the glass network and plays multiple key roles in the present invention. In the present invention, 36%-41% of La2O3 can increase the mechanical strength of the glass, reduce the thermal expansion coefficient, and improve the water resistance. Under the guidance of preliminary theoretical research (such as FNRCS calculation and RSim particle transport simulation, etc.), the inventors found through systematic research that rare earth elements have a relatively high absorption cross-section for fast neutrons, and as a colorless rare earth element oxide, La2O3 can significantly improve the neutron shielding performance while ensuring the transmittance of the glass. In the preferred range of the present invention, the content of La2O3 is 36%-41%, preferably 37%-40%, more preferably 37%-39%, and most preferably 37%-38%. In particular, in some embodiments of the present invention, the content of La2O3 can be any value among 36%, 36.1%, 36.2%, 36.3%, 36.4%, 36.5%, 36.6%, 36.7%, 36.8%, 36.9%, 37%, 37.1%, 37.2%, 37.3%, 37.4%, 37.5%, 37.6%, 37.7%, 37.8%, 37.9%, 38%, 38.1%, 38.2%, 38.3%, 38.4%, 38.5%, 38.6%, 38.7%, 38.8%, 38.9%, 39%, 39.5%, 40%, 40.1%, 40.2%, 40.3%, 40.4%, 40.5%, 40.6%, 40.7%, 40.8%, 40.9%, or 41%, or any range composed of any two of these values, or any value within this range.

[0027] Y2O3 is an external oxide of the glass network and also a colorless rare earth element oxide. In the present invention, 0.5%-4% of Y2O3 can improve the heat resistance, melting temperature, and thermal expansion coefficient of the glass, reduce the thermal shrinkage rate, thereby enhancing the high-temperature resistance performance. Y2O3 can also improve the hardness, abrasion resistance, and corrosion resistance of the glass, and extend the service life. In the preferred range of the present invention, the content of Y2O3 is 0.5%-4%, preferably 1%-4%, more preferably 1%-2%, still more preferably 1.5%-2.5%, and most preferably 1.5-2%. In particular, in some embodiments of the present invention, the content of Y2O3 can be any value among 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4%, or any range composed of any two of these values, or any value within this range.

[0028] Li2O is an external oxide of the glass network. In the present invention, 1%-8% of Li2O can reduce the expansion coefficient of the glass and decrease the crystallization tendency. In particular, as an element with a relatively small atomic number, Li can effectively moderate fast neutrons and is a key fast neutron regulating component in the present invention. In a preferred range of the present invention, the content of Li2O is 1%-8%, preferably 1%-5%, and more preferably 1%-3%. Particularly, in some embodiments of the present invention, the content of Li2O can be any value among 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%, or any range composed of any two of these values, or any value within this range.

[0029] Nb2O5 is an external oxide of the glass network. In the present invention, the introduction of 10%-15% of Nb2O5 can increase the introduction amount of La2O3, significantly improve the crystallization performance of the glass, and ensure the stability of the glass structure. In a preferred range of the present invention, the content of Nb2O5 is 10%-15%, preferably 10%-12%, and more preferably 10%-11%. Particularly, in some embodiments of the present invention, the content of Nb2O5 can be any value among 10%, 10.1%, 10.2%, 10.3%, 10.4%, 10.5%, 10.6%, 10.7%, 10.8%, 10.9%, 11%, 11.1%, 11.2%, 11.3%, 11.4%, 11.5%, 11.6%, 11.7%, 11.8%, 11.9%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%, or any range composed of any two of these values, or any value within this range.

[0030] ZrO2 is an intermediate oxide of glass. In the present invention, no more than 5% of ZrO2 can improve the viscosity, hardness, elasticity, refractive index and chemical stability of the glass, and reduce the thermal expansion coefficient. However, when the content of ZrO2 exceeds 5%, crystallization is likely to occur, so it needs to be carefully controlled. In the preferred range of the present invention, the content of ZrO2 is 0 - 5%, preferably 0 - 2%, more preferably 0 - 1%, most preferably 0 - 0.2%, and further preferably 0 or 0.05 - 0.2%. In particular, in some embodiments of the present invention, the content of ZrO2 can be any value among 0%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.15%, 0.16%, 0.19%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, or any range composed of any two of these values, or any value within this range.

[0031] CeO2 plays a role in improving the ultraviolet absorption ability of the glass in the present invention, keeping the color of the glass stable under strong radiation irradiation, and effectively extending the service life. 0.01% - 0.1% of CeO2 can decompose and release oxygen at the melting temperature, acting as a fining agent to improve the light transmittance. The dosage needs to be appropriately controlled. If it is too little, the fining effect is not obvious; if it is too much, it will cause the glass to change color and reduce the transmittance. In the preferred range of the present invention, the content of CeO2 is 0.01% - 0.1%, preferably 0.05% - 0.1%. In particular, in some embodiments of the present invention, the content of CeO2 can be any value among 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09% or 0.1%, or any range composed of any two of these values, or any value within this range.

[0032] Sb2O3 is used as the main fining agent in the present invention. Its advantages are low toxicity and a lower temperature for the conversion of pentavalent antimony to trivalent antimony compared to white arsenic. In the present invention, when 0.2% - 0.4% of Sb2O3 is used for melting high-density and low-melting-point glass, it can effectively remove bubbles and improve transparency. In the preferred range of the present invention, the content of Sb2O3 is 0.2% - 0.4%, preferably 0.25% - 0.35%, and more preferably 0.25% - 0.3% or 0.3 - 0.35%. In particular, in some embodiments of the present invention, the content of Sb2O3 can be any value among 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39% or 0.4%, or any range composed of any two of these values, or any value within this range.

[0033] In addition to the individual effects of the above components, the present invention also realizes the synergistic optimization of material properties by precisely controlling the proportional relationship between the components. The proportional relationships of these key components and their technical significance will be described in detail below.

[0034] In some embodiments of the present invention, the sum of the contents of SiO2 and B2O3 is not less than 15%, preferably not less than 18%, more preferably not less than 20%, and most preferably not less than 23%. For example, in some preferred embodiments, the sum of the contents of SiO2 and B2O3 is controlled within 19% - 23%. These two main glass-forming oxides, SiO2 and B2O3, jointly construct the glass network skeleton, and their total amount directly affects the basic physical properties of the glass. Through experiments, it is found that when the total amount of SiO2 and B2O3 reaches more than 20%, the glass exhibits better chemical stability and thermal stability; when the total amount reaches 23% and above, as shown in Examples 1, 3, and 4, the thermal expansion coefficient of the glass can be stably controlled within the range of (70 - 76)×10 -7 / °C. Preferably, the mass ratio of SiO2 to B2O3 is 0.08 - 0.5, preferably 0.1 - 0.45, more preferably 0.3 - 0.45 or 0.15 - 0.4. Experiments show that within this proportional range, the thermal neutron absorption ability of B2O3 can be fully exerted, and sufficient structural stability can be provided by an appropriate amount of SiO2, avoiding the physical property defects caused by solely relying on one network former.

[0035] In some embodiments of the present invention, the sum of the contents of BaO, Bi2O3 and SrO is not less than 12%, preferably not less than 15%, more preferably not less than 18%, and most preferably not less than 20%. For example, in some preferred embodiments, the sum of the contents of BaO, Bi2O3 and SrO is 17.5-23%. BaO, Bi2O3 and SrO are the core components providing gamma-ray shielding ability in the present invention. Experiments have shown that when the total amount of these three components reaches 17% and above, the shielding rate of the glass for 60 Co gamma rays can stably exceed 50%; when the total amount reaches more than 20%, as shown in Example 3, the gamma-ray shielding rate can reach 53.4%. Preferably, the mass ratio of BaO to SrO is 1.0-3.5, preferably 1.0-2.5, more preferably 1.5-2.0. Such a specific proportional relationship avoids the problem of decreased chemical stability of the glass that may occur when a large amount of BaO is used alone. At the same time, through the synergistic effect of SrO, while reducing the environmental burden, excellent gamma-ray shielding performance is maintained.

[0036] In some embodiments of the present invention, the sum of the contents of La2O3 and Y2O3 is not less than 30%, preferably not less than 35%, more preferably not less than 38%, and most preferably not less than 40%. For example, in some preferred embodiments, the sum of the contents of La2O3 and Y2O3 is 38%-40%. Under the guidance of preliminary theoretical research (such as FNRCS calculation and RSim particle transport simulation, etc.), the inventors found through systematic research that these two rare earth element oxides have significant absorption ability for fast neutrons. When their total content reaches 38%-40%, the shielding rate of the glass for 252 Cf fast neutrons stably exceeds 50% and does not cause coloring of the glass, maintaining a high transmittance. Preferably, the mass ratio of La2O3 to Y2O3 is 9-82, preferably 15-40, more preferably 19-37. This proportional design makes full use of the main shielding function of La2O3. At the same time, by adding an appropriate amount of Y2O3, the heat resistance and mechanical strength of the glass are enhanced, especially the long-term stability in a high-radiation environment.

[0037] In some embodiments of the present invention, B2O3 and L iThe sum of the contents of B2O3 and Li2O is not less than 12%, preferably not less than 15%, more preferably not less than 18%, and most preferably not less than 20%. For example, in some preferred embodiments, the sum of the contents of B2O3 and Li2O is 18%-24%. These two components, B2O3 and Li2O, form a dual protection mechanism for thermal neutron absorption and fast neutron moderation in the present invention. B2O3 provides the function of thermal neutron absorption, while Li2O effectively moderates fast neutrons through its low atomic number characteristics. When the total amount of the two reaches 18% or more, the glass exhibits neutron shielding ability in the full spectral range; when the total amount reaches 20% or more, as shown in Examples 1 and 4, the neutron shielding rate can reach more than 51%. Preferably, the mass ratio of B2O3 to Li2O is 1.5-25.0, preferably 2.0-20.0, and more preferably 15.0-20.0. Experiments show that too high a content of Li2O may lead to a decrease in the chemical stability of the glass, while too low a content cannot provide sufficient fast neutron moderation effect. This ratio range maintains the long-term use stability of the glass while ensuring the shielding efficiency.

[0038] In some embodiments of the present invention, the content ratio of La2O3 and Nb2O5 in the glass has a significant impact on the comprehensive properties of the glass. The introduction of Nb2O5 can increase the introduction amount of La2O3 and improve the crystallization performance of the glass. By adjusting the content ratio of La2O3 and Nb2O5, the light transmittance performance, radiation shielding performance and physical stability of the glass can be balanced. In the present invention, the content ratio of La2O3 and Nb2O5 is 2.0 - 4.0, more preferably 2.4 - 4.0, relatively preferably 2.4 - 3.8, and still more preferably 3.5 - 3.8. The content ratio of La2O3 and Nb2O5 directly affects the crystallization tendency and overall performance stability of the glass. The introduction of Nb2O5 significantly improves the crystallization problem of the glass with high content of La2O3, and precise control of the ratio of the two is the key to achieving high La2O3 content without sacrificing light transmittance and stability. Excessive Nb2O5 will lead to an increase in the melting temperature, increasing production energy consumption and equipment requirements. More importantly, a high content of Nb2O5 will change the glass network structure, possibly introducing stress centers and reducing the mechanical strength and thermal stability of the glass. In terms of optical properties, excessive Nb2O5 may cause the glass to exhibit a light yellow tone, reducing the transmittance in the short wavelength region, especially in the range of 350 - 450 nm, where the transmittance may decrease significantly. In addition, a high content of Nb2O5 significantly increases the raw material cost, which is not conducive to industrial production. When there is a lack of sufficient Nb2O5 for coordination and stabilization, the glass is prone to crystallization during the cooling process. This crystallization will cause microcrystalline phases to form in the glass, significantly reducing transparency, making the glass appear milky white or translucent, and in severe cases, even preventing the formation of qualified transparent glass products. Crystallization also causes uneven stress distribution inside the glass, increasing the risk of cracking, and reducing the mechanical strength and durability of the glass. In a high-temperature application environment, this instability will further deteriorate, accelerating the aging and performance degradation of the glass. In addition, the imbalance of the La2O3 / Nb2O5 ratio will also affect the long-term service performance of the glass. Especially under continuous radiation conditions, the glass with an inappropriate ratio is more likely to undergo radiation coloring and microstructural changes, resulting in a gradual decrease in the shielding performance and light transmittance over time and shortening the service life. Experiments have shown that when the ratio is 2.4 - 3.8, the glass exhibits better comprehensive properties; especially in the range of 3.5 - 3.8, the comprehensive properties are even better. As shown in Example 3, the glass simultaneously achieves a high neutron shielding rate (52.4%), a gamma-ray shielding rate (53.4%) and good optical transmittance (minimum transmittance 75.6%).

[0039] The precise control and adjustment of the above component ratio relationship form the synergistic mechanism among the components in the present invention, enabling the high-transmittance neutron-gamma composite shielding glass of the present invention to achieve excellent composite radiation shielding performance and long-term stability while maintaining high light transmittance, overcoming the inherent defects of traditional neutron-gamma composite shielding glass in performance balance.

[0040] In some embodiments of the present invention, the high transmittance neutron gamma composite shielding glass comprises the following components in mass percentages: SiO2 3%-7%; B2O3 16%-17%; Al2O3 1%-3%; BaO 11%-12%; Bi2O3 0.5%-5%; SrO 6%-10%; La2O3 37%-38%; Y2O3 1%-2%; Li2O 1%-8%; Nb2O5 10%-15%; ZrO2 0-0.2%; CeO2 0.01%-0.1%; Sb2O3 0.25%-0.35%.

[0041] In some embodiments of the present invention, the high transmittance neutron gamma composite shielding glass comprises the following components in mass percentages: SiO2 5%-7%; B2O3 16%-17%; Al2O3 2%-3%; BaO 11%-12%; Bi2O3 1%-5%; SrO 7%-10%; La2O3 37%-38%; Y2O3 1.5%-2%; Li2O 1%-3%; Nb2O5 10%-12%; ZrO2 0-0.1%; CeO2 0.05%-0.1%; Sb2O3 0.25%-0.35%.

[0042] By precisely controlling the content and proportional relationship of each component, the present invention enables the high transmittance neutron gamma composite shielding glass to simultaneously achieve excellent optical properties, radiation shielding properties, and physical stability, specifically manifested as follows:

[0043] In terms of optical properties, the high transmittance neutron gamma composite shielding glass of the present invention has excellent light transmittance in the visible light wavelength range of 350-900 nm. The maximum transmittance is not less than 85%, the minimum transmittance is not less than 70%, and preferably not less than 75%. This performance index is significantly superior to the common neutron gamma composite shielding glass in the prior art, making the glass material of the present invention have obvious advantages in application scenarios that require both observation and protection functions.

[0044] In terms of radiation shielding properties, the high transmittance neutron gamma composite shielding glass of the present invention exhibits comprehensive composite shielding ability when the thickness is 75 mm: the shielding rate for 252 Cf fast neutrons is not less than 45%, preferably not less than 50%, and more preferably not less than 52%; the shielding rate for 60 Co gamma rays is not less than 45%, preferably not less than 50%, and more preferably not less than 52%. This comprehensive shielding performance that takes into account both fast neutrons and gamma rays realizes effective protection against composite nuclear radiation and meets the extremely complex protection requirements in fields such as the nuclear industry, medical diagnosis, and scientific research.

[0045] In terms of physical stability, the high transmittance neutron gamma composite shielding glass of the present invention exhibits excellent thermal performance indicators: in the temperature range of 20°C - 300°C, the thermal expansion coefficient is controlled within a reasonable range of (65 - 85)×10 -7 / °C, the glass transition temperature is not lower than 550°C, preferably not lower than 600°C, and the sag temperature is not lower than 650°C. These thermal performance indicators ensure the dimensional stability and structural integrity of the glass material in high-temperature environments, greatly expanding its application scenarios and the range of usage conditions.

[0046] The synergistic optimization of the above performance indicators is a technical achievement realized by the present invention through the regulation of component ratios and the optimization of process parameters. In particular, by controlling the contents of compounds such as SiO2, BaO, La2O3, and B2O3 that affect the thermal expansion coefficient of the glass, a high transmittance neutron gamma composite shielding glass with a thermal expansion coefficient of (70 - 80)×10 -7 / °C was prepared; by controlling the contents of BaO, Bi2O3, and SrO, the glass has good gamma-ray shielding performance; by controlling the contents and proportional relationships of La2O3, Li2O, Y2O3, and Nb2O5, the glass has good fast neutron shielding performance; by controlling the content of B2O3, the glass has good thermal neutron absorption performance; by controlling the contents and proportional relationships of La2O3, Y2O3, Nb2O5, Al2O3, and ZrO2, the glass has good chemical stability, high-temperature stability, and mechanical strength.

[0047] Compared with the prior art, the high transmittance neutron gamma composite shielding glass of the present invention achieves efficient composite shielding of gamma rays and fast neutrons while maintaining excellent light transmittance performance, and has good physical and chemical stability, overcoming the technical defects of existing neutron gamma composite shielding glasses in low transmittance, insufficient fast neutron shielding rate, and poor high-temperature stability, providing a new material solution with comprehensive performance and environmental friendliness for the field of nuclear radiation protection.

[0048] In the second aspect of the present invention, a method for preparing the high transmittance neutron gamma composite shielding glass described in the first aspect above is provided, which includes the following steps:

[0049] After mixing the components of the glass material in proportion, a fining agent is added in proportion and mixed evenly; the mixture is melted and stirred; then it is clarified and formed to obtain a glass product.

[0050] In some embodiments of the present invention, the melting temperature is 1200 - 1350°C, and the melting time is 5 - 10 h.

[0051] In some embodiments of the present invention, the stirring speed is 10 - 20 r / min, and the stirring time is 5 - 10 h.

[0052] The stirring method can adopt mechanical stirring and other methods. Mechanical stirring can accelerate the homogenization process of the glass melt. Stirring can continuously divide the inhomogeneous regions and thick stripes in the glass melt into very fine and short stripes, increasing their contact area, which is conducive to the mutual dissolution and diffusion between the glass melt and the stripes, so that the stripes gradually disappear or decrease.

[0053] In the preparation method of the present invention, the clarification is high-temperature clarification, which is carried out after the stirring is completed. Stirring helps to homogenize the glass composition and promote the coalescence of bubbles, and the subsequent high-temperature clarification enables these bubbles to rise to the melt surface and escape more easily. The high-temperature clarification described in the present invention means that the glass liquid is maintained at a high temperature for a period of time to remove the bubbles and incompletely dissolved impurity particles in the molten glass, improving the transparency and quality of the glass. In the present invention, the high-temperature clarification is usually carried out at the melting temperature or slightly higher than the melting temperature. For example, in the temperature range of 1200 - 1350 °C. Specifically, the clarification temperature is usually 20 - 50 °C higher than the melting temperature, using the viscosity reduction caused by the temperature increase to accelerate the rise and escape of bubbles and the dissolution of impurities.

[0054] In the preparation method of the present invention, the time of the clarification process depends on the composition of the glass, the volume of the melt, and the action efficiency of the clarifying agent, and usually needs to last for 1 - 3 hours. After the clarification is completed, the glass temperature gradually decreases to the forming temperature for the forming operation.

[0055] In some embodiments of the present invention, the forming temperature is 900 - 1000 °C, and the forming time is 10 - 20 min. In some embodiments, the present invention adopts a leakage forming process, that is, by controlling the opening of the discharge port at the bottom or side of the furnace, the glass liquid flows into a pre-prepared mold under the action of gravity and forms a preliminary glass blank after cooling. The advantage of this forming method compared with other forming methods (such as pressing forming, blowing forming, etc.) is that it can produce thicker and uniform glass blocks, which is particularly suitable for preparing large-sized shielding glass. This method can also reduce the generation of internal stress, which is beneficial to maintaining the optical quality of the glass.

[0056] After the forming is completed, the glass blank undergoes post-treatment processes such as cutting, grinding, and polishing, and finally a high-transmittance neutron-gamma composite shielding glass product meeting the specification requirements is obtained.

[0057] In the present invention, the precise control of these process parameters, combined with the component ratio design in the first aspect, ensures that the final glass product has excellent optical transmittance, radiation shielding performance, and physical and chemical stability, providing a high-performance transparent protective material for the field of nuclear radiation protection.

[0058] In the third aspect of the present invention, there is provided an application of the high-transmittance neutron-gamma composite shielding glass described in the first aspect above as a neutron and gamma ray shielding material in the fields of medicine, industry, and nuclear industry.

[0059] In the medical field, the shielding glass of the present invention can be used for protective observation windows in radiotherapy rooms, X-ray examination rooms, and radioactive isotope treatment areas. Its high transmittance ensures clear vision for medical staff while providing comprehensive radiation protection. Especially during the operation of 99m Tc, 131 I, 18 F and other radioactive isotopes in the nuclear medicine department, the glass of the present invention can be used as an observation window for the operation box. In proton and neutron therapy facilities, the effective shielding of fast neutrons by the glass of the present invention solves the problem of insufficient protection of traditional lead glass.

[0060] In the nuclear industry field, the shielding glass of the present invention is suitable for observation windows in nuclear power plant control rooms, spent fuel treatment facilities, radioactive waste treatment plants, and protective barriers in nuclear fuel manufacturing and treatment facilities. Its excellent high-temperature stability and suitable thermal expansion coefficient enable it to be used stably for a long time in harsh environments. During the inspection and maintenance of nuclear reactors, the glass of the present invention can be made into a protective screen or a portable observation window. In nuclear accident emergency handling, it can be applied to the observation window of the robot operation system and the protective cover of the camera system.

[0061] In the field of scientific research, the shielding glass of the present invention can be used for observation windows and protective barriers in accelerator facilities, neutron source experimental stations, and synchrotron radiation devices. Its excellent chemical stability ensures that its performance does not decay during long-term use. In neutron scattering and diffraction experiments, the glass of the present invention can be used for sample environment observation windows. In radiochemistry laboratories, it can be used for observation windows of glove boxes and fume hoods.

[0062] In the field of aerospace, the shielding glass of the present invention can be applied to the windows of space stations, satellites, and deep space probes to provide space radiation protection for astronauts and electronic equipment. On high-altitude aircraft, it can be used as a special protective layer for cockpit windows. Its low density and good mechanical strength make it an ideal material for aerospace applications.

[0063] In addition, the shielding glass of the present invention can also be applied to scenarios such as protective windows of industrial non-destructive testing equipment, observation windows of radioactive isotope production facilities, protective screens of high-energy physics experimental devices, protective components of nuclear safety inspection equipment, and special protective equipment in the military field.

[0064] Through the above-mentioned applications in multiple fields and scenarios, the high-transmittance neutron gamma composite shielding glass of the present invention will bring significant improvements to radiation protection technology, solve the deficiencies of existing protective materials in terms of light transmittance, shielding performance and stability, and provide users with safer and more efficient radiation protection solutions.

[0065] The various specific technical features described in the above embodiments of the present invention can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further explain various possible combinations.

[0066] Unless otherwise specified, the numerical range described in the present invention includes all the numerical values ​​within this range, and includes the range value composed of any two numerical values ​​within this range. For example, 0.2-1, this numerical range includes all the numerical values ​​between 0.2 and 1, and includes the range value (0.21-0.9) composed of any two numerical values ​​within this range (for example: 0.21, 0.9); different numerical values ​​of the same indicator appearing in all embodiments of the present invention can be arbitrarily combined to form a range value.

[0067] Compared with the prior art, the advantages of the present invention include:

[0068] The high-transmittance neutron gamma composite shielding glass provided by the present invention achieves an overall improvement in light transmission performance, radiation shielding ability and physical and chemical stability through systematic component design and ratio optimization, and has the following comprehensive advantages over the prior art:

[0069] 1. Overall formula design with synergistic effect of multiple components: The present invention adopts an overall formula design technical means with key components such as La2O3, Nb2O5, BaO, SrO, B2O3 and Li2O as the core, and maintains a specific proportion relationship between the components. It overcomes the technical problems in the prior art that each component has a single function and cannot achieve synergistic effect, and thus achieves a comprehensive technical effect of unifying optical transmittance, radiation shielding and physical stability, so that the material can simultaneously improve the composite shielding ability of gamma rays and neutrons while maintaining high transmittance.

[0070] 2. A new shielding system that takes into account both environmental protection and performance: The present invention constructs an environmentally friendly shielding system that does not rely on traditional PbO. A composite shielding mechanism is formed by a reasonable ratio of multiple components, which overcomes a series of technical problems of existing lead-based shielding glass, such as environmental harm, low light transmittance and poor long-term stability, thereby achieving a technical effect of environmental protection, light transmittance and shielding effectiveness, breaking through the technical bottleneck of traditional cognition that high shielding performance will inevitably lead to low transmittance.

[0071] 3. Multi-dimensional stability balance design: By precisely controlling the content ranges and proportional relationships of each component, the present invention has established a multi-dimensional balance design technical means for thermal stability, chemical stability, and optical stability, solved the technical problem of unstable performance of existing shielding glasses in extremely complex application environments, and thus achieved the technical effect that the material can still maintain structural integrity and functional stability under harsh conditions such as high temperature and strong radiation, greatly extending the service life and application scenarios of the product.

[0072] 4. Industrializable overall preparation process: The present invention has established a complete technical solution from component ratio, melting parameters to forming process, solved the technical obstacle that it is difficult to mass-produce existing high-performance shielding glasses, and thus achieved the technical effect of stable preparation of high-quality and large-size shielding glass products, enabling the effective transformation of theoretical research results into practical products to meet the actual application needs of various fields.

[0073] In the field of the present invention, the preparation of large-size high-transmittance neutron-gamma composite shielding glass does face many technical challenges. Traditional radiation shielding glasses often encounter the following difficulties when increasing the size: First, there are problems of uneven melting during the melting process of special glasses with complex components, especially in systems containing a high proportion of rare earth elements such as La2O3 (36%-41%), and it is easy to form compositional segregation during the melting process, resulting in non-uniform performance of large-size products. Second, the crystallization tendency of the glass system combined with high content of La2O3 and Nb2O5 increases during the cooling process. The larger the size, the more difficult it is to control the temperature gradient, and it is more likely to generate stress non-uniformity, microcracks, and crystallization phenomena, thus affecting the transmittance and mechanical strength of the glass. Third, the difficulty of eliminating bubbles during the melting process of large-size glasses increases. The present invention contains multiple oxide components, and some components may decompose and release gases at high temperatures, such as B2O3, Li2O, etc. If the clarification is not sufficient, bubble defects will be formed in large-size glasses, reducing the light transmittance and shielding performance. Fourth, the technical requirements for uniform annealing of large-size glasses are high. The thermal expansion coefficient of the glass material of the present invention is (70-80)×10 -7 / °C, and the temperature gradient needs to be strictly controlled during the cooling process, otherwise permanent internal stress is easily generated, affecting the optical performance and mechanical strength.

[0074] By precisely controlling the component ratio (especially keeping the La2O3 / Nb2O5 ratio at 3.0-3.8) and adopting an optimized melting process (melting at 1200-1350°C, mechanical stirring at 10-20 r / min for 5-10 h, strictly controlling the forming temperature at 900-1000°C and the forming time at 10-20 min), the present invention effectively solves the above technical problems and successfully realizes the preparation of 300×300×75 mm large-size high-transmittance neutron-gamma composite shielding glass, such as Figure 2As shown. The large-sized glass material prepared in the embodiment simultaneously maintains excellent optical transmittance, radiation shielding performance, and physical stability, providing a reliable guarantee for practical applications.

[0075] 5. Breakthrough improvement in comprehensive performance indicators: Through the systematic optimization of the overall technical solution of the present invention, the limitations of mutual constraints among various performance indicators in the prior art are broken through, and thus comprehensive improvements in the three core indicators of transmittance, shielding performance, and stability are achieved: the minimum transmittance ≥ 75.6% in the visible light wavelength range of 350 - 900 nm, and at the same time, for 252 Cf fast neutrons and 60 Co gamma rays, the shielding rates can both reach more than 50% at a thickness of 75 mm, and it has excellent thermal stability (glass transition temperature ≥ 600 °C). This improvement in overall performance provides a new choice for high-demand application scenarios such as the nuclear industry, medical treatment, and scientific research.

[0076] Through the above overall technical solution, the present invention successfully solves the systematic problems of the existing neutron-gamma composite shielding glass in terms of light transmittance, shielding efficiency, and stability. Synergistic effects are formed among the components, jointly constructing a new type of shielding material with comprehensively improved performance and achieving an overall breakthrough in technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] The specification drawings forming a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. Hereinafter, the embodiments of the present invention will be described in detail in conjunction with the drawings, wherein:

[0078] Figure 1 It is a comparison chart of the transmittance of Comparative Example 1 and Example 3 in the range of 350 - 900 nm.

[0079] Figure 2 It is a physical diagram of a high-transmittance neutron-gamma composite shielding glass of 300 × 300 × 75 mm. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0080] The present invention will be further elaborated in combination with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit its scope. The experimental methods without specifying specific conditions in the embodiments are usually carried out according to conventional conditions or the conditions recommended by the manufacturer.

[0081] Unless otherwise defined, all technical terms and scientific terms used in the present invention shall have the meanings familiar to those skilled in the art. Unless otherwise specified, the reagents or raw materials used in the present invention can be obtained by conventional means and used according to conventional methods or product instructions in the art. In addition, any content similar or equivalent to the methods or materials described can be applied to the methods of the present invention. The preferred embodiments and materials described in the present invention are for illustrative purposes only.

[0082] Examples 1 - 6

[0083] The components of the high-transmittance neutron gamma composite shielding glass of Examples 1-6, the mass percentage of each component, and the physical properties of the prepared glass are shown in Table 1.

[0084] The preparation method is described by taking Example 1 as an example: quartz sand, boric acid, aluminum hydroxide, barium nitrate, strontium carbonate, lanthanum oxide, yttrium oxide, lithium carbonate, niobium pentoxide, zirconium oxide and cerium oxide are used as raw materials, antimony powder as a clarifier is added, and the weight of the clarifier accounts for 0.3% of the weight of the high transmittance neutron gamma composite shielding glass. After being fully mixed, the glass blank is melted at 1350°C for 10 hours, mechanically stirred (20r / min, 5 hours), clarified at high temperature (1370°C, 1 hour), and formed at 900°C (forming time is 10 minutes). The blank is cut and the two large surfaces are ground and polished to a size of 300×300×75mm.

[0085] Examples 2-6 use the same raw material form as Example 1 (such as using quartz sand to provide SiO2, boric acid to provide B2O3, etc.), but according to the specific component ratio of each example (Table 1), the raw materials and their addition amounts are adjusted accordingly. For the case where the component content is 0, the corresponding raw materials are not added. All examples use the same preparation process flow and process parameters.

[0086] Conducted by China Academy of Engineering Physics 60 Co gamma ray shielding test. The test sample size is 300×300×75mm. 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 counts 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.

[0087] Conducted by China Academy of Engineering Physics 252 Cf neutron shielding test. The test sample size is 300×300×75mm. 252The Cf neutron source emits neutrons. The neutron source is installed in a shielding body made of polyethylene. Neutrons are emitted through the collimating holes to form a neutron field. 3 He proportional counter plus PE slowing ball detection. The data acquisition system is composed of electronic plug-ins such as preamplifier, high voltage power supply, single-channel pulse amplifier and counter. Neutron scattering is deducted by shadow cone. Calculate the neutron shielding rate κ of the material. Where N0 is the detector's response count rate to source-directed neutrons and scattered neutrons without test samples; N 0b N is the detector's response count rate to scattered neutrons without test samples; s N is the detector's response count rate of neutrons and scattered neutrons passing through the sample when the test sample is added; sb It is the scattered neutron response count rate of the sample when the test sample is added to the detector.

[0088] The transmittance test was carried out using a UV-visible-infrared spectrophotometer.

[0089] The thermal expansion coefficient of the glass sample was tested using a NETZSCH DIL 402 expansion coefficient tester. Sample preparation: The glass sample was polished into a Φ6×50mm cylindrical glass strip, and the two end faces were parallel. The heating rate was set to 5℃ / min, and the data acquisition cycle was 20ms. The data was plotted as a curve of the relationship between temperature and linear expansion, and the glass transition temperature Tg and the sag temperature Ts were obtained by the tangent method. (GB / T 7962.16~2010)

[0090] Comparative Examples 1 - 10

[0091] The mass percentage of the components of the glass materials of Comparative Examples 1-10 and the physical properties of the prepared glass are shown in Table 1. To ensure the comparability and accuracy of the experimental results, Comparative Examples 1-10 were prepared using the same raw material form, preparation equipment and process parameters as Example 1, that is, the corresponding raw materials were used as starting materials, fully mixed, and then melted at 1350°C for 10 hours, mechanically stirred (20r / min, 5 hours), clarified at high temperature (1370°C, 1 hour), and formed at 900°C (forming time was 10 minutes) to obtain glass blanks. After cutting and grinding and polishing of the two major surfaces, the blanks had a size of 300×300×75mm.

[0092] Table 1 Components, contents and physical properties of shielding glass of Examples 1-6 of the present invention

[0093]

[0094]

[0095]

[0096] Table 2 Composition, content and physical properties of the shielding glasses in Comparative Examples 1-10

[0097]

[0098]

[0099] From the analysis of the experimental results of Examples 1-6 and Comparative Examples 1-10, it can be seen that the present invention has successfully developed a high-performance neutron-gamma composite shielding glass system with complex multi-component synergy. The example group showed excellent performance in three key performance dimensions: the optical transmittance remained at a high level in the wavelength range of 350-900 nm (the minimum transmittance > 75%); in terms of shielding performance, 60 the shielding rates of Co gamma rays and 252 Cf neutrons were both stable above 50%; in terms of thermal properties, the expansion coefficient was controlled below 80×10 -7 / °C, and the glass transition temperature and sag temperature were both maintained in the high-temperature region (Tg > 600 °C, Ts > 650 °C).

[0100] In contrast, most of the samples in the comparative example group had obvious defects: the minimum optical transmittance of Comparative Examples 1-5 was extremely low (5.2-8.3%), indicating serious absorption of the material in the visible light region; Comparative Examples 6-7 verified the key influence of the La2O3 / Nb2O5 ratio on the performance; Comparative Examples 8-9 proved the technical necessity of the B2O3 content range; and Comparative Example 10 demonstrated the influence of the clarifier selection on the optical performance. This precise multi-component ratio design breaks through the technical bottleneck in the traditional understanding that high shielding performance necessarily leads to low transmittance, and successfully realizes the balanced optimization of multi-dimensional performance, providing a new solution of high-performance composite shielding transparent materials for fields such as the nuclear industry and medical radiation.

[0101] In addition, it was found that in the range of melting temperature of 1200-1350 °C, stirring speed of 10-20 r / min, stirring time of 5-10 h, forming temperature of 900-1000 °C, and forming time of 10-20 min, when the component ratio was kept unchanged, the reasonable adjustment of the preparation parameters had little effect on the key performance indicators (optical transmittance, radiation shielding performance, and thermal stability) of the final glass, and the obtained glasses could all achieve the technical effects of the present invention. For example, when the component ratio of Example 3 was melted at 1200 °C, 1300 °C, and 1350 °C respectively, the performance differences of the obtained glasses were all within 3%. This further proves that the core technical contribution of the present invention lies in the design and control of the specific component ratio, and the preparation parameter range of the present application provides a stable and reliable process guarantee for realizing these technical effects.

[0102] In the above-described embodiments of the present invention, the various specific technical features can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0103] The above are only the preferred embodiments of the present invention and are not used to limit the scope of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can still make various modifications to the technical solutions or equivalent replacements of some technical features after reading this specification. Any modification, equivalent replacement or improvement made within the spirit and principle of the present invention shall be regarded as falling within the protection scope of the present invention.

Claims

1. A high transmittance neutron gamma composite shielding glass, characterized in that: The following components are included in mass percentage: SiO22%-7%; B2O316%-25%; Al2O31%-5%; BaO 10%-20%; Bi2O30-5%; SrO 6%-10%; La2O336%-41%; Y2O30.5%-4%; Li2O 1%-8%; Nb2O510%-15%; ZrO20-5%; CeO20.01%-0.1%; Sb2O30.2%-0.4%.

2. The high transmittance neutron gamma composite shielding glass according to claim 1, characterized in that: The invention comprises the following components in mass percentage: SiO2 3%-7%; B2O3 16%-17%; Al2O3 1%-3%; BaO 11%-12%; Bi2O3 0.5%-5%; SrO 6%-10%; La2O3 37%-38%; Y2O3 1%-2%; Li2O 1%-8%; Nb2O5 10%-15%; ZrO2 0-0.2%; CeO2 0.01%-0.1%; Sb2O3 0.25%-0.35%; Preferably, the following components are included in mass percentage: SiO2 5%-7%; B2O3 16%-17%; Al2O3 2%-3%; BaO 11%-12%; Bi2O3 1%-5%; SrO 7%-10%; La2O3 37%-38%; Y2O3 1.5%-2%; Li2O 1%-3%; Nb2O5 10%-12%; ZrO2 0-0.1%; CeO2 0.05%-0.1%; Sb2O3 0.25%-0.35%.

3. The high transmittance neutron gamma composite shielding glass according to claim 1 or 2, characterized in that: The sum of the contents of SiO2 and B2O3 is not less than 15%; Preferably, the mass ratio of SiO2 to B2O3 is 0.08-0.

5.

4. The high transmittance neutron gamma composite shielding glass according to claim 1 or 2, characterized in that: The sum of the contents of BaO, Bi2O3 and SrO is not less than 12%; Preferably, the mass ratio of BaO to SrO is 1.0-3.

5.

5. The high transmittance neutron gamma composite shielding glass according to claim 1 or 2, characterized in that: The sum of the contents of La2O3 and Y2O3 is not less than 30%; Preferably, the mass ratio of La2O3 to Y2O3 is 9-82.

6. The high transmittance neutron gamma composite shielding glass according to claim 1 or 2, characterized in that: The sum of the contents of B2O3 and Li2O is not less than 12%; Preferably, the mass ratio of B2O3 to Li2O is 1.5-25.

0.

7. The high transmittance neutron gamma composite shielding glass according to claim 1 or 2, characterized in that: The content ratio of La2O3 and Nb2O5 is 2.0-4.

0.

8. The high transmittance neutron gamma composite shielding glass according to any one of claims 1 to 7, characterized in that: The glass has a maximum transmittance of not less than 85% in the visible light wavelength range of 350-900nm; Preferably, the glass has a minimum transmittance of not less than 70%, preferably not less than 75%, in the visible light wavelength range of 350-900 nm; Preferably, the glass has a thickness of 75 mm. 252 The shielding rate of Cf fast neutrons is not less than 45%. 60 Co gamma ray shielding rate is not less than 45%; Preferably, the glass has a thickness of 75 mm. 252 Cf fast neutron shielding rate is not less than 50%, 60 Co gamma ray shielding rate is not less than 50%; Preferably, the glass has a thickness of 75 mm. 252 Cf fast neutron shielding rate is not less than 52%, 60 Co gamma ray shielding rate is not less than 52%; Preferably, the thermal expansion coefficient of the glass at 20°C-300°C is (65-85)×10 -7 / ℃, glass transition temperature is not less than 550℃; Preferably, the glass transition temperature of the glass is not less than 600°C, and the relaxation temperature is not less than 650°C.

9. A method for preparing the high-transmittance neutron gamma composite shielding glass according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components of the glass material in proportion, adding a clarifier in proportion, and mixing the mixture; melting and stirring the mixture; and then clarifying and molding the mixture to obtain a glass product; Preferably, the melting temperature is 1200-1350°C and the melting time is 5-10h; Preferably, the molding temperature is 900-1000° C. and the molding time is 10-20 min.

10. Use of the high-transmittance neutron-gamma composite shielding glass according to any one of claims 1 to 8 as a neutron and gamma-ray shielding material in the fields of medicine, industry and nuclear industry.

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