OA22012A

OA22012A - Radiation shielding nano-sized samarium oxide (Sm2O3) doped glass.

Info

Publication number: OA22012A
Application number: OA1202400466
Authority: OA
Inventors: Recep Kurtulus; Taner KAVAS
Original assignee: Gurok Holding B.V
Filing date: 2022-12-14
Publication date: 2025-10-30

Abstract

The invention relates to soda-lime-silica glass doped with radiation shielding nano-sized samarium oxide (Sm2O3), which provides a transparent appearance in different areas where radiation-induced ionizing rays will occur, especially in medical diagnostic centers and research institutes, and can also be used to prevent harmful radiation-induced ionizing rays.

Description

DESCRIPTION

RADIATION SHIELDING NANO-SIZED SM2O3 DOPED GLASS

Technical Field

The invention relates to soda-lime-silica glass doped with radiation shielding nano-sized samarium oxide (SrwOa), which provides a transparent appearance in different areas where radiation-induced ionizing rayswill occur, especially in medical diagnostic centers and research institutes, and can also be used to prevent harmful radiation-induced ionizing rays.

Known State of the Art

As a resuit of the more widespread use of radiation rays due to developments in science, human beings are exposed to radiation much more. The intensity and propagation times of waves, rays and / or similar scattering with different characteristics emitted from different sources such as electronic devices are increasing day by day. Depending on the duration and dose of exposure, this situation can reach a level that threatens human health in a négative way. Especially high-energy radiations such as Xrays and / or gamma rays and / or neutrons and / or similar radiations hâve highly harmful effects on human health. Therefore, there is a direct risk of breaking the main bonds of biological cells. It is also likely to cause health problems in the form of DNA mutations, dry eyes and skin burns. Avoiding exposure to radiation is a vital issue when using radiation sources. For this purpose, different techniques hâve been developed for radiation protection.

Despite the wide use of radiation, the principle called ALARA (As-Low-As-Reasonably Achievable), which forms the basis of radiation protection, has been developed to protect against vital damages. According to this principle, radiation protection requires the lowest possible dose exposure. Reducing radiation exposure dépends on the principles of low exposure time, long distance to the radiation source and armoring the source with appropriate material. The rule that aims to eliminate the effect of the dose by placing material between the radiation source and the people exposed to the dose caused by the source is called the shielding rule. The materials to be used for different types of radiation are also different. The main criteria for shielding harmful émissions from radiation are the intensity, duration and distance of the émission. For radiation

-2shielding material design, different material types and thicknesses are used dependmg on the energy and intensity of the incident radiation.

Lead materials, which are often preferred among the alternative materials preferred to overcome radiation, cause serious négative conséquences on both humans and the environment due to their toxic effect during their production and use. In addition, low neutron absorption capacity and lack of transparency are other shortcomings of lead and concrete-based materials. When it cornes to eliminating the destructive aspects of non-ionizing émissions from radiation, high-density heavy concrète materials with different high-density heavy aggregate additions and varying thicknesses are commonly used to reduce high-energy scattering such as X-rays and / or gamma rays and / or neutrons and / or the like. However, especially during the application and use of these materials, there is a fundamental risk of changes/transformations due to phases in their structure due to time, température, humidity and / or similar influences, as well as risks such as crack formation and / or tearing during casting and use. At the same time, their opaque appearance makes it impossible to use them in applications where backside visibility is essential. Both metallic lead and heavy concrète materials are primary examples of known applications of 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 an inspection door opening, which is a mandatory requirement of the room design criteria. Therefore, in order to overcome the aforementioned problème, different types of glass with various oxide compounds hâve emerged to reduce and / or eliminate the effects of high-energy scattering such as X-rays and / or gamma rays and ! or neutrons and / or the like.

For this purpose, glass materials containing different ratios of lead oxide hâve been developed in order to reduce and / or eliminate the effects of high-energy scattering such as X-rays and / or gamma rays and / or neutrons and / or the like. The high density (9.53 g/cm³) provided by the lead oxide compound was aimed at damping or reflecting back the scattering of radiation incident on the glass material. However, even though a technically successful glass has been developed, due to the toxicity of lead oxide compound to both human health and the environment, glass materials containing lead oxide-free alternatives with the same and / or similar shielding properties hâve corne to the forefront. In terms of alternative glass Systems, although glass types such as

- 3 tellenum oxide, germanium oxide, vanadium oxide-based glass hâve been investigated in terms of literature, they hâve remained incomplète as commercial products. The reasons behind this are; difficulty in accessing raw material sources, their unaffordabiîity in terms of cost, and the fact that they are not considered reasonable within the scope of the known production methods of the art.

There are studies on radiation shielding materials in the literature.

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. Çetin et al.)

The patent application numbered 2018/09709 is related to radiation shielding ΕΓ2Ο3doped borosilicate glass, which can be used as window glass or exterior cladding in buildings, as well as that can also be used in the screens of devices such as computers, mobile phones and TVs that émit radiation. Here, indicators of shielding performance as a resuit of erbium oxide doping at varying ratios were extracted and the doping with the best performance was found.

In the patent application numbered 2018/09707, radiation shielding CeO₂ doped borosilicate glass was presented as the invention. As a resuit of cérium oxide doping at varying rates, indicators of shielding performance were analyzed and the doping with the best performance was found.

European patent application numbered EP1939147A1 relates to a radiation shielding glass and a method for manufacturing the same. The glass composition in question contains 10% to 35% SiO₂, 55% to 80% PbO, 0% to 10% B2O3, 0% to 10% AI2O3, 0% to 10% SrO, 0% to 10% BaO, 0% to 10% Na₂O and 0% to 10% K2O by weight and is stated to hâve a total light transmittance of 50% or more at 400 nm wavelength and 10 mm thickness. However, it does not contain any information on the contribution of nanosized samarium oxide (SmzOs).

In another patent application numbered US10035725B2, a method of producing X-ray and gamma-ray shielding glass is described. The glass composition in question contains 0-35% S1O2, 60-70% PbO, 0-8% B2O3, 0-10% AI2O3, 0-10% Na₂O, 0-10% K2O, 0-0.3% As2O3, 0-2% Sb₂O3, 0-6% BaO; and 0.05-2% ZrÛ2 by weight. However, there is no content for soda-lime-silica glass doped with samarium oxide (Sm2O3).

- 4 As a resuit, due to the above-mentioned drawbacks and the inadequacy of the existing solutions, it has become necessary to develop an improvement in the relevant technical area.

Object of the Invention

The invention is inspired by the current situation and has the objective of solving the above-mentioned problems.

The primary object of the invention is to provide a specially designed lead oxide-free soda-lime-silica glass composition doped with Sm2O3, which protects against highenergy scattering such as X-rays and / or gamma rays and / or neutrons and / or the like, thereby minimizing the négative effects on the environment and human health caused by lead oxide-containing radiation shielding materials used in the art.

One object of the invention is to provide a newly developed transparent nano-sized SmzOa-doped soda-lime-silica glass material with no harmful effects on humans and the environment.

A further object of the invention is to develop a glass material which uses readily available raw materials, is highly cost-effective and is highly adaptable to forming methods.

In order to fulfill the purposes described above, the invention is a radiation shielding lime-silica glass material that can be used to provide a transparent appearance in different areas where radiation-induced ionizing rayswill occur, especially in medical diagnostic centers and research institutes, and can also be used to prevent harmful émissions from radiation, characterized by comprising SiO2, Na2O, CaO, MgO, AI2O3, Fe2Oa and nano-sized Sm20s dopants.

In order to fulfill the purposes described above, the invention relates to a method of manufacturing a radiation shielding soda-lime-silica glass material, characterized by comprising the following process steps:

i. préparation of the raw material composition prescription, ii. weighing and grinding of Silica, Lime and Soda starting raw materials according to the prescription,

-5 ιίι. obtained nano-sized SmzOa powder by calcination of SrmOa powder which obtained by combustion synthesis, iv. mixing of the ground soda-lime-silica raw materials and nano-sized Sm2O3 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 température between 850 and 1200 °C after obtaining a homogeneous mixture, vi. transferring the moîten glass into the forming mold and keeping it at room température, vii. annealing of the final shaped glass products in an annealing furnace at températures between 400 and 700 °C to remove internai stresses.

The structural and characteristic features and ail advantages of the invention will be more clearly understood with the following figures and the detailed description with référencés to these figures, and therefore the évaluation should be made by taking these figures and detailed description into considération.

Figures to Understand the Invention

Figure 1 is a process diagram view of the inventive radiation shielding nano-sized SmzOs doped soda-lime-silica glass.

Figure 2 is a view ofthe test set-up for the subject materiai of the invention.

Description of Part Référencés

1. Raw materiai prescription

2. Weighing unit

3. Raw materiai mixer

4. Melting furnace

5. Forming mold

6. Annealing furnace

7. Glass Product

LS:	Lead shieiding
X:	X-ray source
EXP:	Glass sample
D:	Detector

CS: Computer screen

Detailed Description of the Invention

In this detailed description, a radiation shieiding soda-lime-siiica glass material subject to the invention and the preferred embodiments of the production method are described only for a better understanding of the subject matter.

The invention does not contain lead oxide compared to various existing alternatives and thus does not pose any harm to individual health and the environment. However, it also provides superior radiation shieiding capability at low energy levels compared to lead oxide-free alternatives.

The invention is a radiation shieiding lime-silica glass material that allows a transparent appearance in different areas where radiation-induced ionizing rayswill occur, especially in medical diagnostic centers and research institutes, and can also be used to prevent harmful radiation from radiation, and comprising SiOz, NazCOa, CaO, MgCOs, AI2O3, FezOa and nano-sized SmzOs dopants.

A preferred embodiment of the product of the présent invention comprises the compounds given in Table 1 by weight percent, as well as nano-sized Sm2O3 dopants at 0.005 wt%, 0.05 wt% and 0.5 wt%.

Table 1 Chemical composition of Soda-Lime-Silica glass.

S1O2	NazO	CaO	MgO	AI2O3	FezOs
71.70	14.40	7.95	4.15	1.75	0.05

The linear atténuation coefficient increases with increasing SmzOa doping ratio in the inventive glass material. The highest linear atténuation coefficient is obtained with 0.5 wt% SmzOa doping.

-7The glass material of the invention provides a transparent appearance and the maximum glass thickness is 5 mm.

The invention relates to a method of manufacturing a radiation shielding soda-lime-silica glass material, and comprises the following process steps;

i. préparation of the raw material composition prescription, ii. weighing and grinding of starting Silica, Lime and Soda raw materials according to the prescription, iii. obtained nano-sized SmzOa powder by calcination of SrmCh powder that obtained by combustion synthesis, iv. mixing of the ground soda-lime-silica raw materials and nano-sized Sm2C>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 température between 850 and 1200 °C after obtaining a homogeneous mixture, vi. transferring the molten glass into the forming mold and keeping it at room température, vii. annealing of the final shaped glass products in an annealing furnace at températures between 400 and 700 °C to remove internai stresses.

Our invention relates to a new radiation shielding glass for X-rays and / or gamma rays and / or fast neutrons and / or the like, comprising a nano-sized Sm2Ü3-doped sodalime-silica (SiO₂-Na2CO3-CaO-MgCO3-Al2O3-Al2O3-Fe2O3-Sm2O3) System, which may include Samarium oxide (Sm2O3) dopants. The radiation shielding glass comprises 15 95 mol% SiO₂, 0.01 - 25 mol% Na₂O, 0.01 - 25 mol% CaO, 0.01 - 15 mol% MgO, 0.01 8 mol% AI2O3, 0.01 - 30 mol% SrmOs, and 0.001 -1 mol% Fe2Ü3 as range values.

The process diagram of the inventive radiation shielding nano-sized Sm2O3 doped soda-lime-silica glass is given in Figure 1.

The production method is summarized below;

In the production method of the invention, the raw material prescription is prepared by selecting soda-lime-silica starting raw materials doped with nano-sized SrmOs.

-8First, the selected raw materials are prepared in such a way that they hâve a different glass composition for each different application and different prescriptions. Depending on the tolérance percentage mentioned, weighing and, if necessary, grinding is performed. Samarium (III) Nitrate Hexahydrate [Sm(NO3)3.6H2O] and Glycine

[H_zNCH₂COOH] which is used as fuel, react with combustion synthesis, the SrmOs powder formed after the reaction is subjected to calcination process and at the end of the process, SrmCh powders in oxide form, grain size 50- 300 nm range, 99% purity are obtained. The nano-sized samarium oxide produced by the combustion synthesis method is mixed into the soda-lime-silica glass, which is ground into powder and has an 10 average grain size below 125 pm, and then the mixing process is carried out by means of a mill and / or a mechanical mixer in a dry environment with alumina balls in a porcelain container for 15 to 60 minutes in a rotation speed range of 250 to 500 rpm in order to form a homogeneous mixture.

After obtaining the homogeneous mixture, the prepared glass batches are melted in an 15 electric résistance elevator melting furnace and / or in a gold-platinum alloy crucible without any atmospheric control. In an electric résistance furnace, the mixtures of the samples were melted in a gold-platinum alloy crucible between 850-1200 °C and kept at a maximum température of 60 to 120 minutes.

As soon as the waiting time is over, the obtained glass melt is immediately poured into 20 preferably a graphite mold or kept in a gold-platinum alloy crucible for 5 to 10 minutes at room température. In order to remove the internai stresses of the final shaped glass Products, the glass melt is removed from the mold or gold-platinum alloy crucible and annealed in an annealing pot and / or furnace heated to 400 to 700 °C for 80 to 120 minutes. Upon completion of the waiting period, the glass product is removed from the 25 annealing container and / or furnace and the final glass product is obtained.

The Chemical compositions of the samples prepared for the product of the invention are presented in table 2 in percent by weight.

Table 2 Percentage weights for the prepared recipes

Sample Codes	Soda-Lime-Silica Glass	SmzOs
G1	99.995	0.005

- 9G2 99.950 0.050

G3 99.500 0.500

The radiation shielding nano-sized Sm2O3 doped soda-lime-silica glass samples were obtained after furnace cooling according to the above recipe.

The inventive products were subjected to tests at 40 keV energy level for the 5 détermination of linear atténuation coefficient (μ), which is fondamental among radiation shielding properties. The linear atténuation coefficient was calculated by means of the well-known Beer Lambert équation.

A drawing of the test set-up is presented in Figure 2. It is based on the principle that radiation from an X-ray source travel through the glass sample and is picked up by a 10 detector located behind the glass sample. In the test, the copper element was selected as the X-ray source and the measurement was performed using the HPGe DETECTOR.

The linear atténuation coefficients and mass atténuation coefficients obtained for the produced samples are given in Table 3. Based on the results obtained, it is seen from the increasing linear atténuation coefficient values that the radiation shielding property 15 improves with increasing SrruOa doping.

Table 3 Linear atténuation coefficient measurement results of the samples

Sample Codes	Linear Atténuation Coefficient (cm'¹)
G1	6.36
G2	6.41
G3	6.81

The invention makes it possible to reduce or even eliminate the effect of harmful 20 radiation from radiation for devices operating at the relevant energy level, for example mammography. Thus, any harm to living beings in the environment is prevented. In addition, the absence of lead oxide has a positive impact on both individual health and the environment. In accordance with the régulations and législations, there is an obligation to hâve a section separated by glass material in different areas where

- 10radiation-induced ionizing raysoccurs, especially in medical diagnosis centers and research institutes. From this point of view, it is potential for our invention to become widespread and increase its usability.

A transparent glassware is also at risk of visually bringing out some imperfections, including scratches, bubbles or the like. To achieve a remarkable quality in glassware, it is important to remove defects. The use of an affinity improver is the main parameter that needs to be well controlled. Here, an affinity improver refers to a Chemical compound that supplies clear gas to the melts to enlarge the melt bubbles to be sent away from the melt. Antimony trioxide, arsenic trioxide, sodium chloride, cérium oxide or the like are more preferably used for this purpose. In the présent invention, antimony trioxide and cérium oxide can be added as affinity improvers according to quality requirements.

In our invention, density is a critical parameter which is monitored in a spécifie way. The higher the density of the glass System, the higher the performance of the shielding glass. The densities obtained for these glass composition variations are generally considered to be greater than 2.75- 3.00 g/cm³, preferably 3.00- 3.25 g/cm³, more preferably 3.25- 3.50 g/cm³ and best of ail greater than 3.50 g/cm³. In this study, the densities are greater than 3.25 g/cm³. As a resuit of uniquely designed glass Systems, X-rays and / or gamma rays and / or fast neutrons and / or the like can be efficiently attenuated and / or shielded in a way that alternative shielding materials cannot achieve.

Claims

1. The invention is a radiation shielding soda-lime-silica glass that allows a transparent appearance in different areas where radiation-induced ionizing rays will occur, especially in medical diagnostic centers and research institutes, and at the same time can be used to prevent harmful émissions from radiation, characterized by comprising S1O2, Na2O, CaO, MgO, AI2O3, Fe2Ü3 and nanosized Sm2O3 dopants.

2. The radiation shielding soda-lime-silica glass according to Claim 1, characterized by comprising nano-sized Sm?O3 at 0.005% or 0.05% or 0.5% by weight.

3. The radiation shielding soda-lime-silica glass according to Claim 1, characterized by comprising 15- 95 mol% S1O2, 0.01 - 25 mol% Na2O, 0.01 - 25 mol% CaO, 0.01 - 15 mol% MgO, 0.01 - 8 mol% AI2O3, 0.01 - 30 mol% Srr^Oa, and 0.001 -1 mol% Fe2Û3 as range values.

4. The radiation shielding soda-lime-silica glass according to Claim 1, characterized in that the linear atténuation coefficient increases with increasing SrwOa doping rate in the material.

5. The radiation shielding soda-lime-silica glass according to Claim 1, characterized in that the highest linear atténuation coefficient is obtained with a 0.5 wt% Sm2O3 doping.

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

7. The radiation shielding soda-lime-silica glass according to Claim 1, characterized in that the glass thickness is maximum 5 mm.

8. A radiation shielding soda-lime-silica glass material production method, characterized by comprising the following process steps;

i. préparation of the raw material composition prescription, il. weighing and grinding of Silica, Lime and Soda starting raw materials according to the prescription, iii. obtamed nano-sized Sm2(J3 powder by calcination of SrmOa powder that obtained by combustion synthesis, iv. mixing of the ground soda-lime-silica raw matériels and nano-sized SrmOa 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 température between 850 and 1200 °C, vi. transferring the molten glass into the forming mold and keeping it at room température, vii. annealing of the final shaped glass products in an annealing furnace at températures between 400 and 700 °C to remove internai stresses

9. The production method according to Claim 8, characterized in that; iii) in the process step, Samarium (III) Nitrate Hexahydrate [Sm(NO3)3.6H2O] reacts with Glycine [H₂NCH₂COOH] which is used as fuel, by combustion synthesis, calcination of the SrmCh powder formed after the reaction and at the end of the process, SmzOa powders in oxide form, with a grain size in the range of 50 300 nm, with 99% purity are obtained.

10. The production method according to Claim 8, characterized in that; iv) in the process step, nano-sized samarium oxide obtained by combustion synthesis is doped into the soda-lime-silica raw materials, which are ground into powder and whose average grain size is below 125pm, and a homogeneous mixture is obtained with a mechanical mixer.

11. The production method according to Claim 8 or 10, characterized in that; the mixing process as mentioned in process step iv) is carried out at a rotational speed range of 250 to 500 rpm and for a duration of 15 to 60 minutes.