Glass doped with nano-sized SM2O3 for radiation shielding.

Abstract

Radiation-shielding nano-sized Sm 2 O 3 -doped glass The present invention relates to soda-lime silica glass doped with radiation-shielding nano-sized samarium oxide (Sm 2 O 3 ), which provides a transparent appearance and can also be used to prevent harmful radiation-induced ionizing radiation in various fields where radiation-induced ionizing radiation occurs, particularly in medical diagnostic centers and research institutions.

Description

Technical Field

[0001] The present invention relates to soda-lime silica glass doped with nano-sized samarium oxide (Sm2O3) having radiation shielding properties, which provides a transparent appearance and can also be used to prevent harmful radiation-induced ionizing radiation in various fields where radiation-induced ionizing radiation occurs, particularly in medical diagnostic centers and research institutions.

Background Art

[0002] As a result of the increasing use of radiation due to the evolution of science, humans are exposed to much more radiation. The intensity and propagation time of waves, light rays, and / or similar scatterings with different characteristics emitted from different radiation sources such as electronic devices are increasing daily. Depending on the duration and dose of exposure, this situation can reach a level that threatens human health in a bad direction. In particular, high-energy radiation such as X-rays, and / or gamma rays, and / or neutrons, and / or similar radiation has a very harmful effect on human health. Therefore, there is a direct risk of destroying the main bonds of living cells. It is also likely to cause health problems in the form of DNA mutations, dry eye, and skin burns. Avoiding exposure to radiation is a very serious problem when using radiation sources. For this purpose, different technologies for radiation protection have been developed.

[0003] Despite the widespread use of radiation, the ALARA principle (As-Low-As-Reasonably Achievable), which forms the basis of radiation protection, has developed to protect against extremely serious damage. According to this principle, radiation protection requires the lowest possible dose of exposure. Reducing radiation exposure relies on the principles of short exposure times, long distances to the radiation source, and shielding the source with appropriate materials. Regulations aimed at eliminating the effects of dose by placing materials between the radiation source and people exposed to the dose produced by the source are called shielding regulations. Different types of radiation require different materials. The primary criteria for shielding harmful emissions from radiation are intensity, duration, and distance of emission. For the design of radiation shielding materials, different types and thicknesses of materials are used depending on the energy and intensity of the incident radiation.

[0004] While lead materials are often preferred among favored alternative materials for overcoming radiation, their toxic effects during production and use result in serious adverse consequences for both humans and the environment. In addition, low neutron absorption capacity and lack of transparency are other drawbacks of lead and concrete-based materials. Regarding the elimination of the destructive aspects of non-ionizing emissions from radiation, high-density heavy aggregate adducts and high-density heavy concrete materials of varying thicknesses are commonly used to reduce high-energy scattering, such as X-rays, and / or gamma rays, and / or neutrons. However, particularly during the application and use of these materials, there are fundamental risks of phase-dependent changes / transformations in their structure due to time, temperature, humidity, and / or similar influences, as well as risks of crack formation and / or fracture during casting and use. At the same time, their opaque appearance makes them unsuitable for applications where visibility of the back side is essential. Both metallic lead and heavy concrete materials are primary examples of known applications in the art. However, as mentioned, their lack of transparency and other drawbacks limit their use. In particular, such materials cannot be used for inspection openings, which are a mandatory requirement of room design standards. Therefore, in order to overcome the aforementioned problems, different types of glass with various oxide compounds have emerged to reduce and / or eliminate the effects of high-energy scattering, such as X-rays and / or gamma rays and / or neutrons.

[0005] For this purpose, glass materials containing different proportions of lead oxide have been developed to reduce and / or eliminate the effects of high-energy scattering, such as X-rays and / or gamma rays and / or neutrons. The high density (9.53 g / cm³) provided by the lead oxide compound. 3The purpose of glass was to attenuate or reflect back the scattering of radiation incident on the glass material. However, even though technically successful glass has been developed, due to the toxicity of lead oxide compounds to both human health and the environment, glass materials containing lead oxide-free alternatives that have the same and / or similar shielding properties are gaining importance. Regarding alternative glass systems, types of glass such as tellurium oxide, germanium oxide, and vanadium oxide-based glass have been investigated in the literature, but they remain incomplete as commercial products. The reasons for this are: difficulty in accessing raw material sources, unavailability in terms of cost, and not being considered reasonable within the scope of known manufacturing methods in the art.

[0006] In the literature, there are studies on radiation shielding materials.

[0007] In research found in this art, eggshells and peanut shells were doped into soda-lime silica glass, and their radiation shielding properties were examined (B. Cetin et al.). Patent application 2018 / 09709 relates to radiation-shielding Er2O3-doped borosilicate glass, which can be used as window glass or exterior cladding in buildings, as well as for use in screens of radiation-emitting devices such as computers, mobile phones, and televisions. Here, as a result of doping treatment with various proportions of erbium oxide, an index of shielding performance was extracted, and the doping treatment with the best performance was found.

[0008] Patent application No. 2018 / 09707 presented a borosilicate glass doped with CeO2 for radiation shielding as an invention. The shielding performance was analyzed based on various proportions of cerium oxide doping, and the doping treatment with the best performance was identified.

[0009] European Patent Application EP1939147A1 relates to radiation-shielding glass and a method for producing the same radiation-shielding glass. The glass composition is said to contain 10% to 35% by weight of SiO2, 55% to 80% by weight of PbO, 0% to 10% by weight of B2O3, 0% to 10% by weight of Al2O3, 0% to 10% by weight of SrO, 0% to 10% by weight of BaO, 0% to 10% by weight of Na2O, and 0% to 10% by weight of K2O, and has a total light transmittance of 50% or more at a wavelength of 400 nm and a thickness of 10 mm. However, it does not include any information regarding the contribution of nano-sized samarium oxide (Sm2O3).

[0010] Another patent application, US10035725B2, describes a method for producing glass that shields against X-rays and gamma rays. The glass composition contains 0-35 wt% SiO2, 60-70 wt% PbO, 0-8 wt% B2O3, 0-10 wt% Al2O3, 0-10 wt% Na2O, 0-10 wt% K2O, 0-0.3 wt% As2O3, 0-2 wt% Sb2O3, 0-6 wt% BaO, and 0.05-2 wt% ZrO2. However, there is no mention of soda-lime silica glass doped with samarium oxide (Sm2O3).

[0011] As a result, due to the aforementioned shortcomings and the inadequacy of existing solutions, it has become necessary to develop improvement measures in the relevant technological fields.

[0012] [Purpose of the Invention] This invention arises from the current situation and aims to solve the problems described above.

[0013] The primary objective of the present invention is to provide a specially designed, lead-free, Sm2O3-doped soda-lime silica glass composition that protects against high-energy scattering, such as X-rays and / or gamma rays and / or neutrons, thereby minimizing the adverse environmental and human health effects caused by lead oxide-containing radiation shielding materials used in the art.

[0014] One objective of the present invention is to provide a newly developed, transparent, nano-sized Sm2O3-doped soda-lime silica glass material that has no harmful effects on humans or the environment.

[0015] A further objective of the present invention is to develop a glass material that uses readily available raw materials, is cost-effective, and highly adaptable to various formation methods.

[0016] To achieve the above-mentioned objectives, the present invention provides a radiation-shielding lime silica glass material that can be used to provide a transparent appearance in various fields where radiation-induced ionization rays occur, particularly in medical diagnostic centers and research institutions, and can also be used to prevent harmful emissions from radiation, characterized in that it comprises SiO2, Na2O, CaO, MgO, Al2O3, Fe2O3, and a nano-sized Sm2O3 dopant.

[0017] To achieve the above-mentioned objectives, the present invention provides a method for producing a radiation-shielding soda-lime silica glass material, comprising the following steps: i. The stage of preparing the raw material composition formula, ii. A step of weighing and grinding the starting materials silica, lime, and soda according to the above formulation, iii. A step in which nano-sized Sm2O3 powder is obtained by calcining the Sm2O3 powder obtained by combustion synthesis. iv. The step of mixing the pulverized soda lime silica raw material and the nano-sized Sm2O3 powder in a mill and / or mechanical mixer until a homogeneous mixture is formed. v. After obtaining a homogeneous mixture, the step of melting the mixture in a melting furnace at a temperature between 850 and 1200°C, vi. The step of transferring the molten glass to a mold and holding it at room temperature, vii. Annealing the final-shaped glass product in an annealing furnace at a temperature between 400 and 700°C to remove internal stresses. Relates to a manufacturing method, characterized by comprising

[0018] The structural and characteristic functions and all advantages of the present invention will be more clearly understood from the following figures and the detailed description referring to these figures. Therefore, an evaluation should be made considering these figures and the detailed description.

Brief Description of the Drawings

[0019] [Figure 1] It is a process flow diagram of the soda-lime silica glass doped with nano-sized Sm2O3 with radiation shielding properties of the present invention. [Figure 2] It is a diagram of the test configuration for the target material of the present invention.

[0020] [Explanation of Component Reference Signs] 1. Raw material formulation 2. Weighing unit 3. Raw material mixer 4. Melting furnace 5. Molding die 6. Annealing furnace 7. Glass product LS: Lead shield X: X-ray source EXP: Glass sample D: Detector CS: Computer screen

Modes for Carrying Out the Invention

[0021] In this detailed description, the preferred embodiments of the radiation shielding soda-lime silica glass material and the manufacturing method, which are the objects of the present invention, are described only for a deeper understanding of the subject matter.

[0022] The present invention does not contain lead oxide and thus causes no harm to personal health and the environment compared with various existing alternatives. However, it also provides excellent radiation shielding ability at low energy levels compared with alternatives without lead oxide.

[0023] The present invention relates to a radiation-shielding lime silica glass material, which enables a transparent appearance in various fields where radiation-induced ionization rays occur, particularly in medical diagnostic centers and research institutions, and can also be used to prevent harmful radiation from radiation. It is a radiation-shielding lime silica glass material containing SiO2, Na2CO3, CaO, MgCO3, Al2O3, Fe2O3, and a nano-sized Sm2O3 dopant.

[0024] A preferred embodiment of the product of the present invention contains the compounds shown in Table 1 in weight percentages, as well as 0.005 wt%, 0.05 wt%, and 0.5 wt% of nano-sized Sm2O3 dopant. Table 1: Chemical composition of soda lime silica glass

Table 1

[0025] The glass material of the present invention provides a transparent appearance, and the maximum glass thickness is 5 mm.

[0026] The present invention relates to a method for manufacturing a radiation-shielding soda lime silica glass material, including the following process steps: i. Preparing a raw material composition formulation; ii. Weighing and pulverizing the starting materials of silica, lime, and soda according to the formulation; iii. Obtaining nano-sized Sm2O3 powder by firing the Sm2O3 powder obtained by combustion synthesis; iv. Mixing the pulverized soda lime silica raw material and nano-sized Sm2O3 powder with a mill and / or mechanical mixer until a homogeneous mixture is formed; v. After obtaining a homogeneous mixture, melting the mixture in a melting furnace at a temperature between 850 and 1200 °C; vi. Transferring the molten glass to a molding die and holding it at room temperature; vii. Annealing the final-shaped glass product in an annealing furnace at a temperature between 400 and 700 °C to remove internal stress.

[0027] Our invention relates to a novel radiation-shielding glass comprising a nano-sized Sm2O3-doped soda-lime silica (SiO2-Na2CO3-CaO-MgCO3-Al2O3-Al2O3-Fe2O3-Sm2O3) system for X-rays, and / or gamma rays, and / or fast neutrons, which may contain a samarium oxide (Sm2O3) dopant. The radiation-shielding glass comprises, in the range of values, 15-95 mol% SiO2, 0.01-25 mol% Na2O, 0.01-25 mol% CaO, 0.01-15 mol% MgO, 0.01-8 mol% Al2O3, 0.01-30 mol% Sm2O3, and 0.001-1 mol% Fe2O3.

[0028] Figure 1 shows the process diagram for the radiation-shielding nano-sized Sm2O3-doped soda-lime silica glass of the present invention.

[0029] The manufacturing method is summarized below. In the manufacturing method of the present invention, the raw material formulation is prepared by selecting a soda lime silica starting material doped with nano-sized Sm2O3.

[0030] Firstly, the selected raw materials are prepared to have different glass compositions for different applications and formulations. Weighing and, if necessary, grinding are performed according to the permissible percentages mentioned. Samarium(III) nitrate hexahydrate [Sm(NO3)3.6H2O] and glycine [H2NCH2COOH] used as fuel are reacted by combustion synthesis, and the Sm2O3 powder formed after the reaction is subjected to a calcination process, at which point the Sm2O3 powder in oxide form with a purity of 99% and a particle size in the range of 50-300 nm is obtained. The nano-sized samarium oxide produced by the combustion synthesis method is mixed with soda-lime silica glass that has been ground into powder with an average particle size of less than 125 μm, and then, in a dry environment, a mixing process is carried out using a mill and / or mechanical mixer in alumina balls in a porcelain container at a rotation speed range of 250-500 rpm for 15-60 minutes to form a homogeneous mixture.

[0031] After obtaining a homogeneous mixture, the prepared glass batch is melted without atmosphere control in an electric resistance elevator melting furnace and / or in a gold-platinum alloy crucible. In the electric resistance furnace, the sample mixture is melted in a gold-platinum alloy crucible at a temperature between 850 and 1200°C and held at the maximum temperature for 60 to 120 minutes.

[0032] As soon as the waiting period ends, the resulting molten glass is either immediately poured into a graphite mold, or held at room temperature in a gold-platinum alloy crucible for 5-10 minutes. To remove internal stresses from the final shaped glass product, the molten glass is removed from the mold or gold-platinum alloy crucible and annealed in an annealing pot and / or furnace heated to 400-700°C for 80-120 minutes. Once the waiting period is complete, the glass product is removed from the annealing vessel and / or furnace to obtain the final glass product.

[0033] The chemical composition of the samples prepared for the products of the present invention is shown in Table 2 in weight percent. Table 2 Percentage weight of prepared formulations [Table 2] Soda lime silica glass samples doped with nano-sized Sm2O3 for radiation shielding were obtained after furnace cooling according to the above formulation.

[0034] To determine the fundamental linear attenuation coefficient (μ) among the radiative shielding characteristics, the product of the present invention was tested at an energy level of 40 keV. The linear attenuation coefficient was calculated using the well-known Bouguerambert-Beer equation.

[0035] A diagram of the test setup is shown in Figure 2. It is based on the principle that radiation from an X-ray source travels through a glass sample and is captured by a detector positioned behind the glass sample. In the test, copper was selected as the X-ray source, and the measurements were performed using an HPGe detector.

[0036] Table 3 shows the linear attenuation coefficient and mass attenuation coefficient obtained for the generated samples. Based on the results, it can be seen from the increase in the linear attenuation coefficient that the radiative shielding characteristics improve with increasing Sm2O3 doping. Table 3 Measurement results of the linear attenuation coefficient of the samples [Table 3] This invention makes it possible to reduce or even eliminate the harmful effects of radiation from devices operating at relevant energy levels, such as those used in mammography. Thus, harm to living organisms in the environment is prevented. In addition, the absence of lead oxide has positive effects on both individual health and the environment. According to regulations and laws, various fields where radiation-induced ionization occurs, particularly medical diagnostic centers and research institutions, are required to have areas separated by glass materials. From this perspective, our invention has the potential to become widespread and its usefulness to increase.

[0037] Transparent glassware carries the risk of visually revealing imperfections, including scratches and air bubbles. Eliminating defects is crucial for achieving superior quality in glassware. A key parameter that needs careful control is the use of affinity enhancers. Here, affinity enhancers refer to compounds that supply a transparent gas to the molten material, causing bubbles in the molten material to expand and be expelled. Antimony trioxide, arsenic trioxide, sodium chloride, or cerium oxide are more preferably used for this purpose. In this invention, antimony trioxide and cerium oxide can be added as affinity enhancers according to quality requirements.

[0038] In our invention, density is a very important parameter and is monitored in a specific manner. The higher the density of the glass system, the better the performance of the shielding glass. The densities obtained for these variations of glass composition are generally between 2.75 and 3.00 g / cm³. 3 Preferably 3.00 to 3.25 g / cm³ 3 , more preferably 3.25~3.50 g / cm³3 It is considered to be larger than 3.50 g / cm³, and most preferably 3.50 g / cm³. 3 It is considered to be larger. In this study, the density was 3.25 g / cm³. 3 Larger. As a result of the uniquely designed glass system, X-rays, and / or gamma rays, and / or fast neutrons, etc., can be efficiently attenuated and / or shielded in a way that is not possible with alternative shielding materials.

Claims

1. 71.7% by weight of SiO ２ , 14.4% by weight of Na ２ O, 7.95 wt% CaO, 4.15 wt% MgO, 1.75 wt% Al ２ O ３ , 0.05% by weight of Fe ２ O ３ It also contains 0.005% by weight, 0.05% by weight, or 0.5% by weight of nano-sized Sm ２ O ３ A radiation-shielding transparent soda-lime silica glass comprising a dopant, wherein the Sm2O3 dopant is nano-sized in its raw material state.

2. In the material, as the doping ratio of Sm ２ O ３ increases, the linear attenuation coefficient increases. The radiation-shielding transparent soda-lime silica glass according to claim 1.

3. The highest linear damping coefficient is found in 0.5 wt% Sm ２ O ３ A radiant shielding transparent soda-lime silica glass according to claim 1, obtained by doping treatment.

4. The radiation-shielding transparent soda-lime silica glass according to claim 1, which provides a transparent appearance in the visible light range.

5. The radiation-shielding transparent soda-lime silica glass according to claim 1, wherein the glass thickness is a maximum of 5 mm.

6. A method for producing a material for radiation-shielding transparent soda-lime silica glass according to Claim 1, comprising the following steps: i. The stage of preparing the raw material composition formula, ii. A step of weighing and grinding the starting materials silica, lime, and soda according to the raw material composition formulation described above. iii. Sm obtained by combustion synthesis ２ O ３ By calcining the powder, nano-sized Sm ２ O ３ The stage of obtaining the powder, iv. The pulverized soda lime silica raw material and the nano-sized Sm ２ O ３ The step of mixing the powder in a mill and / or mechanical mixer until a homogeneous mixture is formed. v. The step of melting the mixture in a melting furnace at a temperature between 850°C and 1200°C. vi. The step of transferring the molten glass to a mold and holding it at room temperature, vii. Annealing the final-shaped glass product in an annealing furnace at a temperature between 400 and 700°C to remove internal stresses. A manufacturing method that includes the following features.

7. iii) In the above process step, samarium(III) nitrate hexahydrate [Sm(NO ３ ) ３ 6H ２ O] is used as fuel, glycine [H ２ NCH ２ COOH reacts with the Sm formed after the reaction. ２ O ３ The powder is calcined, and at the end of the above process, Sm in oxide form with a particle size in the range of 50 to 300 nm and a purity of 99% is produced. ２ O ３ The manufacturing method according to claim 6, wherein powder is obtained.

8. iv) The manufacturing method according to claim 6, wherein in the process step, nano-sized samarium oxide obtained by combustion synthesis is doped into the soda lime silica raw material, which has been pulverized into a powder and has an average particle size of less than 125 μm, and a homogeneous mixture is obtained by mechanical mixer.

9. The manufacturing method according to claim 6 or 8, wherein the mixing step mentioned in step iv) is carried out over a duration of 15 to 60 minutes at a rotational speed range of 250 to 500 rpm.

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