Glass doped with nanosized SM2O3 with radiation shielding properties

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 (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.

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 techniques for radiation protection have been developed.

[0003] Despite the widespread use of radiation, the principle called ALARA (As-Low-As-Reasonably Achievable), which forms the basis of radiation protection, has been developed to prevent extremely serious damage. According to this principle, radiation protection requires the lowest possible dose of exposure. The reduction of radiation exposure depends on the principles of short exposure time, long distance to the radiation source, and enclosing the radiation source with appropriate materials. Regulations aimed at eliminating the effect of dose by placing materials between the radiation source and the people exposed to the dose generated by the radiation source are called shielding regulations. The materials used for different types of radiation are also different. The main criteria for shielding harmful emissions from radiation are intensity, duration, and distance of the emissions. For the design of radiation shielding materials, different types and thicknesses of materials are used according to the energy and intensity of the incident radiation.

[0004] Among the preferred alternative materials for overcoming radiation, the lead material, which is often preferred, causes serious adverse effects on both humans and the environment due to its toxic effects during production and use. In addition, low neutron absorption capacity and lack of transparency are other drawbacks of lead- and concrete-based materials. With regard to eliminating the destructive aspects of non-ionizing radiation from radiation, high-density weight aggregate additives with different densities and high-density weight concrete materials with various thicknesses are generally used to reduce high-energy scatterings such as X-rays, and / or gamma rays, and / or neutrons. However, especially during the application and use of these materials, due to time, temperature, humidity, and / or similar effects, there are underlying risks of changes / transformations in the phases in their structures, as well as risks such as crack formation and / or fracture during casting and use. At the same time, their opaque appearance makes it impossible to use them in applications where visibility from the back side is essential. Both metallic lead and weight concrete materials are major examples of known applications in the art. However, as mentioned, their use is limited due to their lack of transparency and other drawbacks. In particular, such materials cannot be used for inspection openings, which are an essential requirement of room design standards. Therefore, to overcome the problems described above, different types of glasses with various oxide compounds have emerged to reduce and / or eliminate the effects of high-energy scatterings 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 scatterings such as X-rays, and / or gamma rays, and / or neutrons. The high density (9.53 g / cm 3) aimed to attenuate or reflect back the scattering of radiation incident on the glass material. However, even though technically successful glasses have been developed, due to the toxicity of lead oxide compounds to both human health and the environment, there is an emphasis on glass materials containing lead oxide-free alternatives and having the same and / or similar shielding properties. Regarding alternative glass systems, glass types such as tellurium oxide, germanium oxide, vanadium oxide based glasses have been explored in terms of literature, but they are still incomplete as commercial products. The reasons are; difficult access to raw material sources, unavailability in terms of cost, and not considered reasonable within the known manufacturing methods of the art.

[0006] There is research in the literature into radiation shielding materials.

[0007] In a study found in the 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 No. 2018 / 09709 describes the radiation shielding Er 2 O 3 The present invention relates to a borosilicate glass doped with erbium oxide, which can be used as window glass or exterior cladding in buildings, as well as for the screens of radiation-emitting devices such as computers, cell phones, and televisions, where an index of shielding performance was extracted as a result of various percentages of erbium oxide doping, and the doping with the best performance was found.

[0008] In patent application No. 2018 / 09707, radiation-shielding CeO 2 The borosilicate glass doped with cerium oxide was presented as an invention. As a result of doping with cerium oxide in various proportions, the indicators of shielding performance were analyzed and the doping with the best performance was found.

[0009] European Patent Application No. EP1939147A1 relates to radiation-shielding glass and a method for manufacturing the same. The glass composition contains 10 wt% to 35 wt% of SiO 2 , 55 wt% to 80 wt% of PbO, 0 wt% to 10 wt% of B2O3, 0 wt% to 10 wt% of Al 2 O 3 , 0 wt% to 10 wt% of SrO, 0 wt% to 10 wt% of BaO, 0 wt% to 10 wt% of Na 2 O, and 0 wt% to 10 wt% of K 2 O, and is stated to have a total light transmittance of 50% or higher at a wavelength of 400 nm and a thickness of 10 mm. However, it does not contain any information about the contribution of nano-sized samarium oxide (Sm 2 O 3 ).

[0010] In another patent application No. US10035725B2, a method for manufacturing glass that shields X-rays and gamma rays is described. The glass composition contains 0 to 35 wt% of SiO 2 , 60 to 70 wt% of PbO, 0 to 8 wt% of B 2 O 3 , 0 to 10 wt% of Al 2 O 3 , 0 to 10 wt% of Na 2 O, 0 to 10 wt% of K 2 O, 0 to 0.3 wt% of As 2 O 3 , 0 to 2 wt% of Sb 2 O 3 , 0 to 6 wt% of BaO, and 0.05 to 2 wt% of ZrO 2 . However, there is no content regarding soda-lime silica glass doped with samarium oxide (Sm 2 O 3 ).

[0011] As a result, due to the above-mentioned drawbacks and the inadequacy of existing solutions, it has become necessary to develop improvement measures in the related technical field.

[0012] [Object of the Invention] The present invention originates from the current situation and aims to solve the above-mentioned problems.

[0013] A main object of the present invention is to provide a lead-free, Sm 2 O 3 -doped soda lime silica glass composition that is specially designed to protect against high-energy scattering, such as X-rays, and / or gamma rays, and / or neutrons, thereby minimizing the adverse effects on the environment and human health caused by radiation shielding materials containing lead oxide used in the art.

[0014] One object of the present invention is to provide a newly developed, transparent, nano-sized Sm 2 O 3 -doped soda lime silica glass material that has no harmful effects on humans and the environment.

[0015] A further object of the present invention is to develop a glass material that uses easily available raw materials, is cost-effective, and has high adaptability to the forming method.

[0016] To achieve the above object, 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 ionizing radiation occurs, particularly in medical diagnostic centers and research institutions, and can also be used to prevent harmful emissions from radiation. In the radiation shielding lime silica glass, it is characterized by comprising SiO 2 、Na 2 O、CaO、MgO、Al 2 O 3 、Fe 2 O 3 、 and nano-sized Sm 2 O 3 dopants.

[0017] To achieve the above object, the present invention provides a method for manufacturing a radiation shielding soda lime silica glass material, comprising the following process steps: i. Preparing the raw material composition prescription ii. Weighing and pulverizing the starting raw materials of silica, lime, and soda according to the prescription iii Obtaining Sm 2 O 3 powder by firing the powder, and obtaining nano-sized Sm 2 O 3 powder iv. Mixing the pulverized soda lime silica raw material and the nano-sized Sm 2 O 3 powder with a mill and / or a 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 melted 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 stress It relates to a manufacturing method, characterized by comprising the above steps.

[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 with reference to these figures. Therefore, an evaluation should be made in consideration of these figures and the detailed description. [Brief Description of the Drawings]

[0019]

Figure 1

Figure 2

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

Best Mode for Carrying Out the Invention

[0021] In this detailed description, preferred embodiments of the radiation-shielding soda lime silica glass material and manufacturing method of the subject 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 does not cause any harm to personal health and the environment compared to various existing alternatives. However, it also provides excellent radiation shielding ability at low energy levels compared to alternatives that do not contain lead oxide.

[0023] The present invention is a radiation-shielding lime silica glass material that enables a transparent appearance and can also be used to prevent harmful radiation from radiation in various fields where radiation-induced ionizing radiation occurs, particularly in medical diagnostic centers and research institutions. It contains SiO 2 , Na 2 CO 3 , CaO, MgCO 3 , Al 2 O 3 , Fe 2 O 3 , and a radiation-shielding lime silica glass material containing a nano-sized Sm 2 O 3 dopant.

[0024] Preferred embodiments of the product of the present invention are the compounds shown in Table 1 in weight percent, and 0.005 wt%, 0.05 wt%, and 0.5 wt% of nano-sized Sm 2 O 3 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. The step of preparing a raw material composition prescription; ii. The step of weighing and pulverizing the starting raw materials of silica, lime, and soda according to the prescription; iii. The Sm obtained by combustion synthesis 2 O 3 By firing the powder, nano-sized Sm 2 O 3 To obtain a powder; iv. The pulverized soda-lime silica raw material and nano-sized Sm 2 O 3 The powder is mixed with a mill and / or a mechanical mixer until a homogeneous mixture is formed; v. After obtaining a homogeneous mixture, the mixture is melted in a melting furnace at a temperature between 850 and 1200 °C; vi. The molten glass is transferred to a molding die and held at room temperature; vii. To remove internal stress, the final-shaped glass product is annealed in an annealing furnace at a temperature between 400 and 700 °C.

[0027] Our invention relates to a novel radiation-shielding glass with a nano-sized Sm 2 O 3 doped soda-lime silica (SiO 2 -Na 2 CO 3 -CaO-MgCO 3 -Al 2 O 3 -Al 2 O 3 -Fe 2 O 3 -Sm 2 O 3 ) system, which may contain a samarium oxide (Sm 2 O 3 ) dopant. The radiation-shielding glass has, as a range value, 15 to 95 mol% of SiO2 and 0.01 to 25 mol% of Na 2 2O, 0.01 to 25 mol% of CaO, 0.01 to 15 mol% of MgO, 0.01 to 8 mol% of Al 2 2O 3 2O, 0.01 to 30 mol% of Sm 2 2O 3 2O, and 0.001 to 1 mol% of Fe 2 2O 3 are provided.

[0028] The process flow diagram of the radiation-shielding nano-sized Sm 2 2O 3 -doped soda-lime silica glass of the present invention is shown in FIG. 1.

[0029] The manufacturing method is summarized below. In the manufacturing method of the present invention, a raw material formulation is prepared by selecting a nano-sized Sm 2 2O 3 -doped soda-lime silica starting material.

[0030] First, the selected raw materials are prepared to have different glass compositions for different uses and different formulations. Weighing and, if necessary, grinding are carried out according to the mentioned allowable percentages. Samarium(III) nitrate hexahydrate [Sm(NO 3 ) 3 .6H 2 2O] and glycine [H 2 2NCH 2 2COOH] used as a fuel react by combustion synthesis, and the Sm 2 2O 3 powder formed after the reaction is subjected to a firing process, and finally, Sm in the form of an oxide with a particle size in the range of 50 to 300 nm and a purity of 99% 2 2O 3A powder is obtained. The nano-sized samarium oxide produced by the combustion synthesis method is mixed with soda-lime silica glass having an average particle size of less than 125 μm, which has been pulverized into a powder, and then, in a dry environment, in an alumina ball in a porcelain container, at a rotation speed range of 250 to 500 rpm for 15 to 60 minutes, the mixing process is carried out by a mill and / or a mechanical mixer 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 mixture of the sample 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] Immediately after the waiting time ends, the obtained glass melt is preferably immediately poured into a graphite mold or held at room temperature in a gold-platinum alloy crucible for 5 to 10 minutes. To remove the internal stress of the final-shaped glass product, the glass melt is taken out of the mold or the gold-platinum alloy crucible and annealed in an annealing pot and / or furnace heated to 400 to 700 °C over 80 to 120 minutes. When the waiting period is completed, the glass product is taken out of the annealing container and / or furnace, and the final glass product is obtained.

[0033] The chemical composition of the sample prepared for the product of the present invention is presented in weight percent in Table 2. Table 2 Percentage weight of the prepared formulation

Table 2

[0034] In order to determine the fundamental linear attenuation coefficient (μ) among the radiation shielding characteristics, the product of the present invention was tested at an energy level of 40 keV. The linear attenuation coefficient was calculated by the well-known Bouguer–Lambert–Beer's law.

[0035] A drawing of the test configuration is presented 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 element was selected as the X-ray source and the measurement was carried out using an HPGe detector.

[0036] The linear attenuation coefficient and mass attenuation coefficient obtained for the produced samples are shown in Table 3. Based on the obtained results, it can be seen that the radiation shielding characteristics improve with the increase in Sm 2 O 3 doping treatment, from the increase in the linear attenuation coefficient values. Table 3 Measurement results of the linear attenuation coefficient of the samples

Table 3

[0037] A transparent glassware also has a risk that any imperfection, including scratches and bubbles, becomes visually apparent. To achieve excellent quality of the glassware, it is important to remove defects. The main parameter that needs to be well controlled is the use of an affinity improver. Here, the affinity improver refers to a compound that supplies a transparent gas to the melt, expands the bubbles in the melt, and expels them from the melt. Antimony trioxide, arsenic trioxide, sodium chloride, or cerium oxide, etc. are more preferably used for this purpose. In the present invention, antimony trioxide and cerium oxide can be added as affinity improvers according to the quality requirements.

[0038] In our invention, density is a very important parameter and is monitored in a specific way. The higher the density of the glass system, the higher the performance of the shielding glass. The densities obtained for these variations in glass composition are generally considered to be greater than 2.75~3.00 g / cm 3 , preferably greater than 3.00~3.25 g / cm 3 , more preferably greater than 3.25~3.50 g / cm 3 and most preferably considered to be greater than 3.50 g / cm 3 . In this study, the density is greater than 3.25 g / cm 3 . 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 cannot be achieved with alternative shielding materials.

Claims

1. In various fields where radiation-induced ionizing rays are generated, particularly in medical diagnostic centers and research institutions, a radiation-shielding soda-lime silica glass that enables a transparent appearance and can be used to prevent harmful emissions from radiation. In this glass, SiO ２ , Na ２ O, CaO, MgO, Al ２ O ３ , Fe ２ O ３ , and a nano-sized Sm ２ O ３ -doped radiation-shielding soda-lime silica glass.

2. Nano-sized Sm ２ O ３ The radiation-shielding soda-lime silica glass according to claim 1, comprising 0.005% by weight, or 0.05% by weight, or 0.5% by weight thereof.

3. As range values, 15 to 95 mol% of SiO ２ , 0.01 to 25 mol% of Na ２ O, 0.01 to 25 mol% of CaO, 0.01 to 15 mol% of MgO, 0.01 to 8 mol% of Al ２ O ３ , 0.01 to 30 mol% of Sm ２ O ３ , and 0.001 to 1 mol% of Fe ２ O ３ The radiation-shielding soda-lime silica glass according to claim 1, comprising

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

5. The highest linear attenuation coefficient is 0.5 wt% of Sm ２ O ３ The radiation shielding soda lime silica glass according to claim 1, obtained by doping treatment with

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

7. The radiation-shielding soda-lime silica glass according to claim 1, wherein the glass thickness is at most 5 mm.

8. A method for manufacturing a radiation-shielding soda-lime silica glass material, comprising the following process steps: i. Preparing a raw material composition formulation; ii. Weighing and pulverizing starting materials of silica, lime, and soda according to the raw material composition formulation; iii Sm obtained by combustion synthesis ２ O ３ By firing the powder, a nano-sized Sm ２ O ３ powder is obtained, iv. mixing the ground soda lime silica raw material and the nano-sized Sm ２ O ３ powder with a mill and / or a mechanical mixer until a homogeneous mixture is formed v. 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 glass product of the final shape in an annealing furnace at a temperature between 400 and 700 °C to remove internal stress. A manufacturing method comprising these steps.

9. iii) In the step stage, samarium(III) nitrate hexahydrate [Sm(NO ３ ), ３ . ６ H ２ O] reacts with glycine [H ２ NCH ２ COOH] used as fuel by combustion synthesis, and after the reaction, the Sm ２ O ３ powder is fired, and finally, at the end of the step stage, Sm ２ O ３ powder in the form of an oxide with a purity of 99% in the particle size range of 50 to 300 nm is obtained. The manufacturing method according to claim 8.

10. iv) In the said process steps, the 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 a mechanical mixer. The manufacturing method according to claim 8.

11. The manufacturing method according to claim 8 or 10, wherein the mixing process mentioned in process step iv) is carried out over a duration of 15 to 60 minutes in a rotational speed range of 250 to 500 rpm.

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