WO2023282545A1 - 무납 감마선 차폐 시트 및 이의 제조방법 - Google Patents

무납 감마선 차폐 시트 및 이의 제조방법 Download PDF

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Publication number
WO2023282545A1
WO2023282545A1 PCT/KR2022/009471 KR2022009471W WO2023282545A1 WO 2023282545 A1 WO2023282545 A1 WO 2023282545A1 KR 2022009471 W KR2022009471 W KR 2022009471W WO 2023282545 A1 WO2023282545 A1 WO 2023282545A1
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Prior art keywords
rubber
shielding sheet
weight
parts
lead
Prior art date
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Ceased
Application number
PCT/KR2022/009471
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English (en)
French (fr)
Korean (ko)
Inventor
안동진
심연하
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Rasgo Co ltd
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Rasgo Co ltd
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Application filed by Rasgo Co ltd filed Critical Rasgo Co ltd
Priority to JP2023580985A priority Critical patent/JP2024526276A/ja
Publication of WO2023282545A1 publication Critical patent/WO2023282545A1/ko
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals

Definitions

  • the present invention relates to a lead-free gamma-ray shielding sheet and a method for manufacturing the same, and more particularly, to a lead-free gamma-ray shielding sheet that is not heavy and provides a high gamma-ray shielding rate, and a method for manufacturing the same.
  • Radioactive materials including those that exist in nature and those that are artificially made for use in industry and medicine.
  • Ionizing radiation refers to radiation such as alpha, beta, protons, neutrons, gamma rays, and X-rays that cause ionization when passing through materials. There is no need for shielding, and beta rays are known to be larger than alpha rays, but in general, thin aluminum foil or plastic plates can block them.
  • gamma rays are electromagnetic waves generated from nuclear decay or transformation and have higher energy than X-rays, and are characterized by very strong penetrating power.
  • each photon of medical X-rays is about 2,000 eV
  • cosmic gamma rays are usually about 10 million eV (10 MeV) to 300 billion eV (300 GeV)
  • gamma rays have 10,000 to 100 million times the energy of X-rays.
  • the density or thickness must be higher than that of the X-ray shielding material to block gamma rays.
  • Korean Patent Publication No. 10-2014-0086201 discloses a first metal sheet (lead) of a metal thin film for shielding gamma rays and a second metal sheet (cadmium) of a metal thin film for shielding neutrons as a shielding body for shielding radiation generated from a nuclear reactor. are starting As in the above Korean Patent Publication, thick lead sheets and heavy water are generally used as gamma ray shielding agents in nuclear reactors. Also, it was common for workers working at nuclear power plants to wear lead gowns.
  • lead gowns are used in the form of sheets by dispersing lead components in polyvinyl chloride resin (PVC) and then extruded, but they are heavy, weighing about 5 kg to 10 kg, resulting in poor wearing comfort and poor activity.
  • PVC polyvinyl chloride resin
  • lead is a heavy metal and is highly hazardous, so it is not easy to dispose of it.
  • Korean Patent Registration No. 10-1605319 discloses a rubber composition for radiation shielding comprising 80 to 200 parts by weight of tungsten powder and 5 to 50 parts by weight of additives in 100 parts by weight of acrylonitrile-butadiene rubber (NBR).
  • Korean Patent No. 10-1804295 discloses a radiation shielding rubber containing 80 to 200 parts by weight of tungsten powder, 100 to 300 parts by weight of tantalum powder, and 5 to 50 parts by weight of additives in 100 parts by weight of acrylonitrile-butadiene rubber (NBR). composition is disclosed.
  • Korean Patent No. 10-1804295 discloses adipic acid ether ester type (RS-107) to prevent agglomeration of metals such as tungsten powder and tantalum powder when using a large amount of metal. Tungsten powder and tantalum powder are coated with a plasticizer (Claim 1).
  • An object of the present invention is to provide a sheet having a high gamma ray shielding rate without using lead.
  • the present invention provides a shielding sheet usable as a shield, blanket, or protective clothing for shielding gamma rays in a nuclear power plant.
  • the kneading step is related to a method for manufacturing a gamma ray shielding sheet, which is a step of mixing 600 to 1900 parts by weight of tungsten with 100 parts by weight of rubber.
  • the gamma ray shielding sheet relates to a gamma ray shielding sheet containing 600 to 1900 parts by weight of tungsten and 5 to 15 parts by weight of antimony oxide relative to 100 parts by weight of rubber.
  • the radiation shielding sheet manufactured in the present invention has a gamma ray (Cs-137) shielding rate of 10.3% (thickness 1.1mm) and 18.6% (thickness 2.2mm), respectively, and the gamma ray (Cs-137) of a conventionally marketed product (see FIG. 1). 137) It is about 10 times higher than the shielding rate of 4% (thickness of 4mm) (comparison converted to the same thickness).
  • the sheet of Example 1 is very thin with a thickness of 1.1 mm, it has a high shielding rate and can provide a protective product with excellent wearing comfort.
  • the gamma ray shielding sheet of the present invention increases the gamma ray shielding rate by uniformly dispersing tungsten in the sheet even though high-density tungsten is used in a large amount (600 to 1900 parts by weight relative to 100 parts by weight of base rubber).
  • the gamma ray shielding sheet manufacturing method of the present invention maintains the temperature of the mixing roll roller and the mixed solid material (rubber + tungsten) at 35 to 40 ° C and 75 to 85 ° C, respectively, and repeatedly feeds the mixed solid material to the mixing roll, thereby producing a large amount of tungsten. It can be evenly dispersed in rubber.
  • Figure 2 is a schematic diagram of the Soviet and kneading device.
  • Figure 3 is a photograph of the mixed solids that have undergone the kneading process.
  • Example 4 is a vulcanized final product (sheet (1, 1 mm) of Example 1).
  • the lead-free gamma ray-shielding sheet of the present invention includes a kneading step, a kneading step, a sheet manufacturing step (calendar step), and a vulcanization step.
  • the Soviet step is a step of crushing and pulverizing the rubber by putting the solid rubber into a mixing roll.
  • the molecular chains of the raw rubber eg, raw rubber
  • a mixing roll eg, a kneader
  • the viscoelasticity is lowered by lowering the degree of polymerization by releasing the twist between the molecules in the chain state. It is a process that reduces the fineness and increases the plasticity.
  • the solid rubber may be at least one of natural rubber, styrene butadiene rubber, nitrile butadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, and butadiene rubber.
  • the mixing roll used in the mixing step and the kneading step refers to a facility capable of crushing or compressing rubber with two rolls. Referring to FIG. 2 , the mixing roll rotates two rollers in opposite directions and crushes solid rubber when it is introduced between the rollers.
  • the kneading step is a step in which tungsten and additives are introduced into the mixing roll and mixed with the rubber (see FIG. 2A).
  • the mixing roll may be the same as or different from the mixing roll of the Soviet stage.
  • the tungsten is a high density (19.25 g/cm 3 ), high specific gravity metal. In the present invention, 600 to 1900 parts by weight of tungsten is used relative to 100 parts by weight of rubber.
  • the content of tungsten is less than 600 parts by weight, the gamma ray shielding rate is low, and if it exceeds 1900 parts by weight, uniform dispersion is difficult in the kneading step, and it is difficult to extrude to a certain thickness in the calendering process.
  • tungsten having a purity of 97% to 99.9% and a particle size (particle size) of 0.01 ⁇ m to 100 ⁇ m may be used.
  • the additive used in the kneading step may be zincating (using zinc oxide), an oxidizing agent (vulcanizing agent), or a mixture thereof.
  • the oxidizing agent may be sulfur, a thiocarabmate accelerator, a Thjuram or Thiourea accelerator.
  • the additive may be mixed in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of rubber.
  • the gamma ray shielding sheet of the present invention may increase elasticity, tear strength, and tensile strength as well as durability by mixing additives such as zinc oxide with rubber.
  • flame retardant antimony oxide may be additionally mixed with 100 parts by weight of rubber.
  • the particle size (particle size) of the antimony oxide may be 0.1 ⁇ m to 100 ⁇ m.
  • the antimony oxide increases the flame retardancy of the gamma ray shielding sheet.
  • the mixed solid material may be repeatedly compressed and dispersed with the mixing roll several times.
  • a process of cutting the mixed solid material that has passed through the mixing roll and reintroducing it into the mixing roll may be repeated several times so that tungsten is uniformly dispersed in the rubber.
  • the mixed solid is a mixture including rubber, tungsten, additives, antimony oxide, and the like, and is not a liquid state but a solid state paste that maintains viscosity.
  • the surface temperature of the mixing roll in the kneading step may be 35 to 40 ° C, and the temperature of the mixed solids attached to the surface of the roll may be 75 to 85 ° C.
  • the surface temperature of the roll exceeds 40 ° C. and rotates for a long time, the rubber to be compressed is easily ripened or scorch occurs (a phenomenon in which the properties of the rubber change due to curing under undesirable conditions). Therefore, the present invention maintains the temperature of the mixed solid at 75 to 85 ° C while adjusting the surface temperature of the roll in the range of 35 to 40 ° C. When the temperature of the roll and the solid mixture is lower than the above temperature, sufficient dispersion is difficult.
  • the manufacturing method of the gamma ray shielding sheet of the present invention may further include an aging step of cutting the mixed solid material in the form of a sheet that has passed through the kneading step into a predetermined thickness and size and storing it for a predetermined time.
  • the aging step may be 12 hours or more, preferably 24 hours or more.
  • the aging step may be performed at room temperature.
  • Mixed solids that have not undergone the aging step may cause a problem in that the defect rate is high or the product life is shortened over time.
  • the sheet manufacturing step is a step of compressing the mixed solid material produced in the kneading step to a certain thickness using a rolling roll.
  • a sheet in the sheet manufacturing step, can be manufactured with a constant thickness using a calender (equipment in which two rolling rolls are attached to the top and two to the bottom in an inverted L shape).
  • a calender equipment in which two rolling rolls are attached to the top and two to the bottom in an inverted L shape.
  • the aged and hardened mixed solid (shielding body) is put into a kneader and made into a paste state with heat and pressure.
  • the surface temperature of the kneader roll and the surface temperature of the mixed solid material (shielding body) are maintained at 35 to 40 ° C. and 75 to 85 ° C., respectively, to prevent scorching and the like.
  • a mixed solid material maintained at 75 to 85° C. may be injected into the rolling roll of the calender.
  • the roll surface temperature of the rolling roll may be 35 to 40 ° C, and the temperature of the mixed solids attached to the roll surface may be 75 to 85 ° C.
  • the curing step is a step of vulcanizing the sheet by putting it into a rolling roll.
  • the vulcanization step is a step in which additives such as sulfur and rubber react by applying heat and pressure to the compressed sheet using a device called Rotor Q.
  • the sheet manufactured through the vulcanization step may be a gamma ray shielding sheet having excellent durability and elasticity.
  • tungsten can be uniformly dispersed in rubber by repeating the kneading step of maintaining a specific temperature several times despite the use of a large amount of high-density tungsten.
  • the present invention relates to a lead-free gamma ray shielding sheet.
  • the lead-free gamma ray shielding sheet of the present invention is a sheet formed by dispersing a large amount of tungsten in base rubber.
  • the base rubber is at least one of natural rubber, styrene butadiene rubber, nitrile butadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, and butadiene rubber.
  • the sheet may include 600 to 1900 parts by weight of tungsten based on 100 parts by weight of the base rubber.
  • the tungsten may have a purity of 97% to 99.9% and a particle size (particle size) of 0.01 ⁇ m to 100 ⁇ m.
  • the lead-free gamma ray shielding sheet of the present invention may include additives and antimony oxide.
  • the additive may be zincating (using zinc oxide), an oxidizing agent (vulcanizing agent) or a mixture thereof.
  • the additive may be mixed in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of rubber.
  • the antimony oxide may be additionally mixed in an amount of 5 to 15 parts by weight based on 100 parts by weight of rubber.
  • the additives and antimony oxide may refer to the above-described contents.
  • the aged and hardened mixed solid was put into a kneader, and the surface temperature of the kneader roll and the mixed solid (shield) were maintained at 35 to 40 ° C and 75 to 85 ° C, respectively, to form a paste.
  • the mixed solid material kneaded from the kneader was calendered (4 rolls) and compressed to a certain thickness.
  • the sheet compressed to a certain thickness was vulcanized using a device called Rotor Cure. Two sheets of 1.1 mm and 2.2 mm thickness were finally obtained.
  • Example 4 to 7 are test reports of the gamma ray shielding sheet prepared in Example 1.
  • the gamma ray (Cs-137) shielding rate of Example 1 was 10.3% (thickness: 1.1 mm), respectively.
  • As 18.6% (thickness 2.2mm) it is about 10 times higher than the gamma ray (Cs-137) shielding rate of 4% (thickness 4mm) of a commercially available product (see FIG. 1) (comparison converted to the same thickness).
  • the sheet of Example 1 is very thin with a thickness of 1.1 mm, it has a high shielding rate and can provide a protective product with excellent wearing comfort.
  • the present invention can be used as a gamma ray shielding sheet.
  • the shielding sheet of the present invention can be applied to protective products with excellent wearing comfort.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
PCT/KR2022/009471 2021-07-06 2022-06-30 무납 감마선 차폐 시트 및 이의 제조방법 Ceased WO2023282545A1 (ko)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023580985A JP2024526276A (ja) 2021-07-06 2022-06-30 はんだなしガンマ線遮蔽シート及びこれの製造方法

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KR10-2021-0088194 2021-07-06
KR1020210088194A KR102334663B1 (ko) 2021-07-06 2021-07-06 무납 감마선 차폐 시트 및 이의 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102334663B1 (ko) * 2021-07-06 2021-12-07 안동진 무납 감마선 차폐 시트 및 이의 제조방법
KR20240138247A (ko) 2023-03-10 2024-09-20 김현태 무납 감마선 차폐시트

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160010729A (ko) * 2014-07-17 2016-01-28 서울대학교산학협력단 표면을 고분자로 둘러싼 텅스텐입자를 함유하는 우수한 차단특성을 가진 납이 없는 다층구조 복합 방사선 차폐재 및 이의 제조 방법
WO2016185997A1 (ja) * 2015-05-15 2016-11-24 岩宮　陽子 放射線遮蔽シート、およびその製造方法
KR101890267B1 (ko) * 2017-03-07 2018-10-01 라스고 주식회사 무납 방사선 차폐 시트의 제조방법
KR20200013180A (ko) * 2018-07-26 2020-02-06 라스고 주식회사 무납 방사선 차폐 시트 및 이의 제조방법
KR102334663B1 (ko) * 2021-07-06 2021-12-07 안동진 무납 감마선 차폐 시트 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160010729A (ko) * 2014-07-17 2016-01-28 서울대학교산학협력단 표면을 고분자로 둘러싼 텅스텐입자를 함유하는 우수한 차단특성을 가진 납이 없는 다층구조 복합 방사선 차폐재 및 이의 제조 방법
WO2016185997A1 (ja) * 2015-05-15 2016-11-24 岩宮　陽子 放射線遮蔽シート、およびその製造方法
KR101890267B1 (ko) * 2017-03-07 2018-10-01 라스고 주식회사 무납 방사선 차폐 시트의 제조방법
KR20200013180A (ko) * 2018-07-26 2020-02-06 라스고 주식회사 무납 방사선 차폐 시트 및 이의 제조방법
KR102334663B1 (ko) * 2021-07-06 2021-12-07 안동진 무납 감마선 차폐 시트 및 이의 제조방법

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JP2024526276A (ja) 2024-07-17
KR102334663B9 (ko) 2025-04-18

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