KR20160142634A - Radiation sheilding composition and method for preparing the same - Google Patents
Radiation sheilding composition and method for preparing the same Download PDFInfo
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- KR20160142634A KR20160142634A KR1020150078620A KR20150078620A KR20160142634A KR 20160142634 A KR20160142634 A KR 20160142634A KR 1020150078620 A KR1020150078620 A KR 1020150078620A KR 20150078620 A KR20150078620 A KR 20150078620A KR 20160142634 A KR20160142634 A KR 20160142634A
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- 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
- G21F1/10—Organic substances; Dispersions in organic carriers
- G21F1/103—Dispersions in organic carriers
- G21F1/106—Dispersions in organic carriers metallic dispersions
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
The present invention relates to a radiation shielding composition having improved durability and gamma ray shielding performance of a sheet and a method for producing the same.
The radiation shielding composition of the present invention can increase the content of the shielding material and the hydrolysis resistance by using ultra high molecular weight polyurethane. In addition, the radiation shielding composition of the present invention includes a polyetheretherketone (PEEK) resin and a nano-clay (clay) to enhance the durability of the sheet. In addition, the radiation shielding composition of the present invention encapsulates water having the best neutron shielding ability, and thus can exhibit superior performance to neutron shielding. In addition, the present invention can maintain the gamma ray shielding ability even when exposed to a long time radiation including a polyether ether ketone (PEEK) resin.
Description
More particularly, the present invention relates to a radiation shielding composition having improved durability and gamma ray shielding performance of a sheet and a method for producing the composition.
Radiation has existed since the Earth was created, and now we are living in an environment full of radiation. Radioactive materials exist in nature, artificially made for industrial and medical use, and there are many kinds.
Ionization refers to radiation such as alpha, beta, protons, neutrons, gamma rays, X-rays that cause ionization when passing through matter. Alpha rays are also absorbed and blocked by materials with thickness of paper. , While beta rays are known to be larger than alpha rays, but they can usually be blocked by thin aluminum foils or plastic plates.
On the other hand, the gamma ray is an electromagnetic wave which is generated from collapse or transformation of nucleus and has higher energy than X-ray. These gamma rays can be blocked through high-density metal materials such as concrete or iron and lead. However, when metal materials are used, there arises a problem that the weight of the shielding material is increased due to high density of these materials.
Neutrons are generated when the nucleus collapses or breaks, and it has no charge. However, since a high-speed neutron has a large energy of 1 MeV or more, a material containing a large amount of hydrogen having a mass similar to that of a neutron is used And a neutron shielding material mixed with a neutron absorbing material for absorbing thermal neutrons having a reduced energy of the high-speed neutron is required.
In particular, gamma rays or neutrons can act directly on the atom or molecule to change the main structure of DNA or protein, and when acting on the reproductive cells of an organism, it can increase the probability of inducing mutations and induce malformations, It is possible to cause diseases such as cancer, and in addition, thermal neutrons have the problem of radioactively polluting the surrounding environment by radiating the surrounding substances. Therefore, in the field where radiation is applied, a radiation shielding material capable of shielding gamma rays or neutrons harmful to the human body and the environment is indispensably required. It is known that a conventional gamma ray shielding material can obtain a gamma ray shielding effect by using a material including iron, lead, and cement.
Neutron shielding materials include neutron shielding materials such as paraffin, carbon, boron, boron, lithium, gadolinium, etc. which have a high content of light atomic numbers such as hydrogen (H), oxygen (O) It is known to use a compound containing a material having a large thermal neutron absorption cross-section in a polymer or metal base.
X-rays discovered by Rutgen are now widely used both industrially and medically. However, when such radiation is exposed to the human body, radiologists, schools, research institutes, and nuclear power plant workers operating medical doctors and X- Due to the nature of the work, it can be continuously exposed to radiation.
It is exposed to the risk of cancer and other diseases such as leukemia and other diseases by inducing damage of human DNA and chromosome due to long-term exposure to harmful radiation. As radiation exposure is physically harmful to humans, workers in the field should always use shielding materials that can block radiation.
The lead robe, which is worn as protective clothing for conventional radiation shielding, is used as a sheet-like material after dispersing lead components in vinyl chloride resin (PVC) and rubber (rubber) It is heavy with 5 ~ 10 ㎏, poor fit, poor activity, and little wear.
Swedish Patent No. 349366 (1960), which uses barium sulfate in conventional radiation shielding fibers, discloses a method of artificially introducing into bare fibers. However, since a small amount of barium sulfate can be added in polymer synthesis, And the durability of the fiber is drastically reduced. US Pat. No. 3,239,669 discloses that there is a disadvantage of human harmfulness by using lead. In US Pat. No. 3,192,439, a wire made of an alloy is used in a fiber form There is a disadvantage in that the flexibility as a fiber is poor. Russian Patent No. 10-2000-7003445 discloses a method of dispersing metal particles to prepare a mixture and binding it to the surface of a fiber. But it does bind to the surface of the fiber. There is a disadvantage that it is difficult to exhibit durability as a method.
Japanese Patent Specification No. 2008-538136 proposes a technique using shielding material of tungsten, barium sulfate and bismuth as a shielding material, and it is applicable as a shielding material for medical use due to the shielding effect against X-ray and gamma ray. However, There is a problem that it can not be a suitable material to be applied as a shielding material of a nuclear power plant in which radiation of a kind occurs.
Korean Patent Laid-Open Publication No. 10-2004-0093878 discloses a technique for manufacturing radiation shielding fibers by using an organic iodine-based material such as barium sulfate. However, since there is no harmfulness to human body caused by lead and it is advantageous to achieve weight reduction, And barium sulphate itself is not excellent in shielding effect against gamma rays or X-rays. In the patent document 10-2010-0047510, a technique of mixing a nanoparticle-sized radiation shielding material into a polymer is introduced, and metal nanoparticles are used However, the use of metal nanoparticles at a ratio of up to 20% relative to the total polymer makes it possible to improve the dispersion ratio of the polymer even though the dispersion effect is excellent. Is high and the pore size is large. Therefore, considering the high permeability of radiation Part of the surface shielding effect and insufficient, it is oxidized boron neutron shielding (B 2 O 3) a neutron shield having a broad energy distribution by using a single material has a limit economical as high is to apply to the fiber the nano metal particles But it is not compatible with.
In Patent Application No. 1988-0012950, there is a problem in weight and human hazard in the method of manufacturing radiation shielding fiber. In application No. 10-2006-0070088, shielding fiber is introduced through wet radiation method using barium sulphate (BaSO 4 ) It is impossible to increase the content of the polyolefin in a state of being made into a state of yarn, and there is a limitation in shielding, and a series of techniques such as application No. 10-2009-0010508,10-2009-0010581, 10-2009-0010642, It has a high hydrogen atom density and paraffin mixing, but it is advantageous for neutron shielding, but it has a disadvantage that it is weak against the bonding force with fibers. Therefore, it is not suitable for use because it is not durable as protective clothing or fiber. X-ray), and the introduction technique 20-1999-0023705 discloses a method of using a porous absorber to reduce particle radiation About alpha is insufficient for effective, or other radiation. In addition, Korean Patent No. 10-2004-0048588 discloses a radiation shielding material that does not use lead, but uses antimony trioxide (Sb 2 O 3 ) and tin (Sn) powder. These materials have disadvantages .
In addition, techniques for various metal materials and polymers for shielding radiation from radiation shielding fibers have been disclosed. However, many studies have been carried out on techniques for preventing the deterioration or damage of shielding materials from progressing rapidly when exposed to radiation for a long period of time . Further, there is still a demand for a technique that can more effectively shield neutrons as well as radiation such as alpha, beta, proton, gamma ray, and X-ray.
It is an object of the present invention to solve the above-mentioned problems, and it is an object of the present invention to solve the above-mentioned problems, and to provide a polyetheretherketone (PEEK) resin without using lead to irradiate not only radiation such as alpha, beta, proton, gamma ray, Shielding composition and a method for producing the same.
The present invention provides a composition and a shielding material for preventing rapid deterioration or damage of a shielding material caused by radiation.
The present invention
A base resin comprising at least one member selected from the group consisting of a polyurethane resin, a polysiloxane resin, a silicone resin, a fluororesin, an acrylic resin, and an alkyd resin;
A neutron shielding material comprising at least one selected from the group consisting of water capsules, polyvinyl alcohol (PVA), medium density polyethylene (MDPE), high density polyethylene (HDPE), and low density polyethylene (LDPE);
Polyetheretherketone (PEEK) for improved durability and
The present invention relates to a radiation shielding composition comprising at least one additive material selected from the group consisting of a metal powder, a metal oxide powder, a paraffin, a boron compound and a carbon powder.
The present invention also relates to a base resin comprising at least one member selected from the group consisting of a polyurethane resin, a polysiloxane resin, a silicone resin, a fluororesin, an acrylic resin and an alkyd resin; A neutron shielding material comprising at least one selected from the group consisting of water capsules, polyvinyl alcohol (PVA), medium density polyethylene (MDPE), high density polyethylene (HDPE), and low density polyethylene (LDPE); And polyether ether ketone (PEEK) for improving durability to prepare a composition;
Adding a solvent to the composition to adjust dispersion and viscosity of the composition;
Adding at least one additive selected from the group consisting of metal powder, metal oxide powder, paraffin, boron compound, carbon powder and nano-sized clay to the composition; And
And a step of coating the composition on the object.
The present invention also relates to a sheet for radiation shielding formed by coating a radiation shielding composition according to any one of the preceding claims.
The present invention also relates to a textile and a radiation-shielding textile composite comprising the textile and the radiation-shielding sheet formed on the textile.
The radiation shielding composition of the present invention can increase the content of the shielding material and the hydrolysis resistance by using ultra high molecular weight polyurethane. In addition, the radiation shielding composition of the present invention includes a polyetheretherketone (PEEK) resin and a nano-clay (clay) to enhance the durability of the sheet. In addition, the radiation shielding composition of the present invention encapsulates water having the best neutron shielding ability, and thus can exhibit superior performance to neutron shielding. In addition, the present invention can maintain the gamma ray shielding ability even when exposed to a long time radiation including a polyether ether ketone (PEEK) resin.
1 is a cross-sectional view of a radiation-shielding textile composite of the present invention.
2 is a cross-sectional view of another radiation shielding textile composite of the present invention.
Hereinafter, embodiments and examples of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.
It is to be understood, however, that the following description is not intended to limit the invention to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof is contemplated by one or more other features But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
First, the radiation shielding composition of the present invention will be described.
The radiation shielding composition of the present invention comprises a base resin, a neutron shielding material, polyetheretherketone (PEEK) and an additive material.
The base resin forms a shielding film or a sheet layer.
The base resin may be at least one selected from the group consisting of a polyurethane resin, a polysiloxane resin, a silicone resin, a fluororesin, an acrylic resin, and an alkyd resin.
The base resin is preferably a polyurethane resin. The polyurethane resin is excellent as a shielding material because of its excellent bonding strength with a fiber material, high durability and excellent flexibility. Also, the hydrogen density is high, which is effective for decelerating high-speed neutrons. Further, the polyurethane has an advantage of excellent bonding strength with a fiber material, high durability, and excellent flexibility.
The polyurethane resin is preferably an ultrahigh molecular weight polyurethane having a number average molecular weight of 30,000 to 80,000 g / mol. The ultrahigh molecular weight polyurethane of the present invention is 3 to 4 times more than the molecular weight of polyurethane used for conventional shielding.
The polyurethane includes polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 650 to 3,000 g / mol and polyethylene glycol (PEG) having a number average molecular weight of 30,000 to 40,000 g / mol (A) and isocyanate (B) at a molar ratio of 1: 1.5 to 5.5 (A: B) can be used.
The polyurethane used as the base film for shielding is generally a polyol having a number average molecular weight of 1,000 to 2,500 g / mol. However, the polyol used in the present invention is composed of polytetramethylene ether glycol (PTMEG) having a molecular weight of 650 to 3,000 g / mol and polyethylene glycol (PEG) having a molecular weight of 30,000 to 40,000 g / mol Component is introduced to prepare an ultrahigh molecular weight polyurethane.
The polyurethane of the present invention can be represented by the following general formula (1).
And R < 2 > is a linear or branched alkyl group having 2 to 20 carbon atoms.
The R2 may be represented by the following formula (2).
The polyurethane resin of the present invention is represented by the following formulas (1) and (2).
[Equation 1]
6? (Total number of carbon atoms / number of ETHER bonds)? 9
&Quot; (2) "
0.036? (Number of methyl groups / total number of carbon atoms)? 0.1
The ultrahigh molecular weight polyurethane resin of the present invention has a higher hydrogen density and is effective for decelerating high-speed neutrons. In addition, the ultrahigh molecular weight polyurethane resin can increase the density of the base film layer to increase the content of the radiation shielding material, and is also excellent in radiation resistance and hydrolysis resistance.
The neutron shielding material may be at least one selected from the group consisting of water capsules, polyvinyl alcohol (PVA), medium density polyethylene (MDPE), high density polyethylene (HDPE), and low density polyethylene (LDPE). Preferably, a water capsule is used as the neutron shielding material.
The water capsules may be formed of a core containing water and a shell layer surrounding the coater, and the shell may be formed of a polymer such as epoxy (EPOXY). The shell uses a pore size of the polymer shell smaller than that of the water molecule so that water can not be evaporated and discharged.
As a neutron shielding material, water is best known as a material. However, there is a problem that it is difficult to carry or contain water in the sheet or film. The composition of the present invention may contain water in a radiation shielding sheet or film layer using water capsules containing water.
The water capsules may be dispersed in an organic solvent and added to the base resin. Since the shell is formed of a hydrophobic material, the water capsule can be well dispersed in the organic solvent and the base resin.
The water capsules may contain 5 to 10 parts by weight based on 100 parts by weight of the base resin.
The water capsules may have a size of 0.4 to 0.7 mu m.
The specific gravity of the medium density polyethylene which can be used as the neutron shielding material is 0.926 to 0.940, the specific gravity of the high density polyethylene is 0.941 or more, and the specific gravity of the low density polyethylene is 0.925 or less.
The polyetheretherketone (PEEK) can enhance the durability and gamma ray shielding ability of the film or sheet layer formed by the composition.
The polyetheretherketone (PEEK) has a similar chemical structure and is more durable than the polyetherketone (PEK), which is known to have a radiation-resistant effect, with an equivalent radiation resistance effect.
More specifically, the CEK double bond of benzene ring plays an important role in the radiation resistance of the PEK resin. In the case of C = C double bond, when the radiation collides, the energy of the radiation is C = C double bonds of π → π *, and the remaining radiation energy causes destruction of PEK.
The PEEK of the present invention has one more benzene ring in the unit than the PEK, and thus can have greater durability against radiation.
The PEEK usable in the present invention may have a weight average molecular weight of 100,000 to 150,000.
The additive material may be selected from the group consisting of a metal powder, a metal oxide powder, a paraffin, a boron compound and a carbon powder, and preferably two or more kinds may include other additive materials. The additive material may be an inorganic material having a relatively high electron density or an organic inorganic material having an excellent radiation shielding performance.
The metal powder may use a metal having a relatively high electron density. For example, the metal powder may be aluminum, titanium, zirconium, scandium, yttrium, cobalt, tantalum, molybdenum, tungsten, or the like.
The metal oxide powder may be at least one of palladium oxide, iridium oxide, ruthenium oxide, osmium oxide, rhodium oxide, platinum oxide, iron oxide, nickel oxide, cobalt oxide, indium oxide, aluminum oxide, potassium oxide, titanium oxide, Can be used.
The metal powder and the metal oxide powder may be used in the form of a composite.
The metal powder and the metal oxide powder may have a particle diameter of 0.01 to 100 탆.
The paraffin is a straight chain paraffinic hydrocarbon (CH 3 (CH 2 ) n CH 3 ), which is rich in carbon atoms, and the boron compound is suitable for shielding neutrons because of its large cross-sectional area of fine absorption and wide energy distribution. In order to shield neutrons, it is preferable that the content of light atoms such as hydrogen, oxygen, and carbon is high, which is similar in mass to neutrons.
The boron compound may be selected from the group consisting of boric acid (H 3 BO 3 ), colemanite (Ca 2 O 14 B 6 H 10 ), zinc borate (Zn 2 O 14 , 5H 7 B 6 , Zn 4 O 8 B 2 H 2 And Zn 2 O 11 B 6 ), boron carbide (B 4 C), boron nitride (BN), boron oxide (B 2 O 3 ), and the like. More preferably, it can be used as a composite material of zinc borate and boron carbide.
The carbon powder may be fullerene, carbon nanofibers, carbon nanotubes, or the like. The carbon powder preferably has a particle diameter of 5 to 200 nm.
The carbon nanofibers have a high linear expansion coefficient, a specific heat of 0.7 KJ / kg and excellent thermal properties. In addition, the nano-activated carbon fiber (NCF) has nano-size micropore distributed on the surface, and thus has a larger surface area than that of activated carbon, and evenly disperses pores, Do. That is, the nano-carbon fiber has a high absorption cross-sectional area of 1,000 ± 50 m 2 / g, which can effectively shield neutrons.
The composition of the present invention may contain 5 to 30 parts by weight of the neutron shielding material, 5 to 30 parts by weight of the polyether ether ketone (PEEK), and 1 to 80 parts by weight of the additive material, based on 100 parts by weight of the base resin.
If the neutron shielding material is less than 5 parts by weight, the neutron shielding effect may be lowered. If the neutron shielding material is more than 30 parts by weight, the neutron shielding material may have low bonding strength with the fibers or may be difficult to be applied as a shielding material. .
More preferably, the additive material comprises 5 to 80 parts by weight of a metal powder, 1 to 70 parts by weight of a metal oxide powder, 1 to 50 parts by weight of paraffin, 5 to 15 parts by weight of a boron compound, 10 to 50 parts by weight of at least one of them.
The radiation shielding composition may further comprise 1 to 80 parts by weight of an inorganic additive based on 100 parts by weight of the first resin. Examples of the inorganic additive include calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate, barium chloride, barium sulfate and the like. Such an inorganic additive is preferably safe for the human body, has excellent radiation shielding effect, and has a high density. The inorganic additive preferably has a particle diameter of 0.01 to 100 탆.
The radiation shielding composition may further comprise 10 to 100 parts by weight of a curing agent based on 100 parts by weight of the first resin. In this case, the radiation shielding composition is preferably a two-liquid composition, and when the base resin comprises at least one of a thermosetting resin, a polyurethane resin, a polysiloxane, a fluororesin, and an alkyd resin, the radiation curable composition preferably includes the curing agent. Further, the composition of the present invention may further include a catalyst for promoting curing.
The composition may further include 10 to 50 parts by weight of nano-sized clay to improve the bonding strength between the base resin and the additive, based on 100 parts by weight of the base resin.
The clay may be bentonite.
The clay has a high viscosity, so that the binding force between the additive material, particularly inorganic particles, and the base resin can be increased. Accordingly, when the composition is formed into a sheet or a film, the durability of the resin is enhanced and the resin density is high, thereby improving the radiation shielding effect.
The composition may further comprise 1 to 5 parts by weight of polymethyl urea powder having a size of 2 to 10 탆 to 100 parts by weight of the base resin so as to increase the crosslinking density of the base resin.
In another aspect, the present invention relates to a method of producing a radiation shielding sheet. The sheet manufacturing method includes a composition preparation step, a dispersion and viscosity control step, an additive material addition step and a coating step.
The step of preparing the composition is a step of preparing a composition by mixing a base resin, a neutron shielding material and polyetheretherketone (PEEK). The above-mentioned contents can be referred to for the content and the content of the base resin and the like to be mixed. The base material or the neutron shielding material may be used by dissolving in alcohol or methyl ethyl ketone organic solvent.
The dispersion and viscosity control step may include adding one or more solvents selected from the group consisting of isopropyl alcohol (IPA), methyl ethyl ketone (MEK), toluene (TOLUENE), dimethylformamide (DMF), and xylenes (XYLENE) Can be adjusted. The dispersion and viscosity control step may facilitate the coating processability and thickness control by controlling the addition amount of the solvent.
The method comprises adding to the composition at least one additive selected from the group consisting of metal powder, metal oxide powder, paraffin, boron compound, carbon powder and nano-sized clay. In the above step, the inorganic additive may be further added and mixed.
The additive materials, the clay and the inorganic additive can be mentioned in the above description.
The method includes coating the composition on an object. The method also includes the step of applying heat to the composition to cure the composition.
Such objects include all materials, articles, and devices that require radiation shielding. The object may include fiber textiles, plastic, glass, and the like.
The curing can be carried out using known methods.
In another aspect, the present invention relates to a radiation shielding sheet formed by coating the radiation shielding composition.
Figures 1 and 2 are schematic cross-sectional views of a radiation-shielding textile composite of the present invention. Hereinafter, the textile composite for radiation shielding of the present invention will be described with reference to FIGS. 1 and 2. FIG.
The radiation shielding textile composite of the present invention may comprise a textile and the radiation shielding sheet formed on the textile.
The textile may comprise a fabric, a knitted fabric, a nonwoven fabric, or the like.
Specifically, as shown in FIG. 1, an adhesive layer may further be provided between the textile and the radiation shielding sheet.
Specifically, the radiation-shielding textile composite comprises: a textile; An adhesive layer disposed on the textile; And a radiation shielding sheet disposed on the adhesive layer may be sequentially stacked.
Also as the case may be, as shown in Figure 2, the radiation-shielding textile composite comprises a first textile; A first adhesive layer disposed on the first textile; A radiation shielding sheet disposed on the first adhesive layer; A second adhesive layer disposed on the radiation shielding sheet; And a second textile disposed on the second adhesive layer are sequentially laminated.
The textile may include polyester fibers, nylon fibers, and aramid fibers, but the scope of the present invention is not limited thereto.
As described above in the description of the radiation shielding composition of the present invention, in the case of using a two-liquid composition containing a curing agent, a separate adhesive layer for bonding the textile and the radiation shielding sheet can be omitted. Specifically, the radiation shielding sheet may be adhered to the textile by semi-drying, and then the textile may be bonded and heated to completely dry and bond.
The radiation shielding textile composite may be applied to all kinds of textile such as a radiation shielding bag, protective gear, protective clothing, etc., which require radiation shielding.
Hereinafter, the structure of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
Example 1
5 parts by weight of medium-density polyethylene (MDPE) as a polyethylene powder, 10 parts by weight of high-density polyethylene (HDPE), 5 parts by weight of low-density polyethylene (LDPE) resin (KKPC) were mixed.
Thereafter, a polyether ether ketone (PEEK) (VICTREX 90P grade:
4 parts by weight of molybdenum powder (AO Metal Co., Ltd.), 3 parts by weight of tantalum powder (AO Metal Co., Ltd.), 35 parts by weight of tungsten oxide (WO 3 ) powder (AO Metal Co., Ltd.) , And 5 parts by weight of an inorganic additive, barium sulfate (BaSO 4 ) (manufactured by Solvay Co.) were preliminarily mixed.
Subsequently, 13 parts by weight of paraffin, 8 parts by weight of boron carbide (B 4 C) and 25 parts by weight of nano carbon fiber (CD7097U grade, manufactured by Colombia Chemical Co.) were added to 100 parts by weight of the polyurethane resin, Solution.
The solution containing the radiation shielding composition was coated on a release paper to a thickness of 150 μm by a dam coater to prepare a radiation shielding film, which was then dried and cured at 130 ° C. for 50 seconds. Thereafter, 100 parts by weight of a polyurethane adhesive resin (two-component type of a homogeneous chemical D-ACE 5038B) and 10 parts by weight of a curing agent (homogeneous chemical D-ACE575), 20 parts by weight of DMF, 20 parts by weight of MEK Followed by mixing to prepare an adhesive, and the adhesive was applied to a thickness of 50 mu m using a comma knife. A fabric containing polyester fibers was laminated on the adhesive and dried and cured at 130 캜 for 50 seconds to prepare a radiation-shielding textile composite.
Example 2
10 parts by weight of medium density polyethylene as a polyethylene powder, 5 parts by weight of high density polyethylene (HDPE) and 5 parts by weight of low density polyethylene (LDPE) resin (KKPC) were mixed with 100 parts by weight of a polyurethane resin.
Thereafter, the polyetheretherketone resin was mixed with 30 parts by weight of the same product as that of Example 1 in an amount of 30 parts by weight based on 100 parts by weight of the polyurethane resin. To 100 parts by weight of the polyurethane resin, 20 parts by weight of methyl ethyl ketone (MEK) And 20 parts by weight of dimethylformamide (DMF) were further added to prepare a first preliminary composition.
10 parts by weight of molybdenum powder, 10 parts by weight of tantalum powder, 20 parts by weight of tungsten oxide (WO 3 ) powder as a metal oxide powder, and 5 parts by weight of barium sulfate (BaSO 4 ) as an inorganic additive were added to the primary preliminary composition Lt; / RTI >
Thereafter, 25 parts by weight of paraffin, 5 parts by weight of boron carbide (B 4 C), and 15 parts by weight of nano carbon fiber of the same product as that of Example 1 were added to and mixed with 100 parts by weight of the polyurethane resin to prepare a radiation shielding composition Solution.
The same procedure as in Example 1 was carried out except that the solution containing the radiation shielding composition was used in the release film in place of the dam coater thickness of 150 탆 in the thickness of 350 탆 and the adhesive in the thickness of 50 탆 instead of 20 탆, Textile composites were prepared.
Example 3
100 parts by weight of a curing agent (Shin Yatsu SVS 12,000-B), 10 parts by weight of a medium density polyethylene powder, 5 parts by weight of a low density polyethylene powder and 5 parts by weight of a high density polyethylene powder were mixed with 100 parts by weight of a silicone resin (ShinYeatsu SVS 12,000-A).
Then, 5 parts by weight of polyether ether ketone was mixed with 100 parts by weight of the silicone resin, and 20 parts by weight of methyl ethyl ketone (MEK) and 30 parts by weight of toluene were added to 100 parts by weight of the silicone resin To prepare a first preliminary composition.
4 parts by weight of molybdenum powder, 10 parts by weight of tantalum powder, 60 parts by weight of tungsten oxide (WO 3 ) powder as a metal oxide powder, and 10 parts by weight of barium sulfate (BaSO 4 ) as an inorganic additive were added to the primary preliminary composition Lt; / RTI >
Subsequently, 5 parts by weight of paraffin, 8 parts by weight of boron carbide (B 4 C), and 10 parts by weight of the same nano carbon fiber as Example 1 were added to and mixed with 100 parts by weight of the silicone resin main body to prepare a solution containing the radiation shielding composition .
The solution containing the radiation shielding composition was coated on a release paper to a thickness of 100 μm by a dam coater to prepare a radiation shielding film and dried at 110 ° C. for 40 seconds to remove the film surface from the semi- -Dry), the fabric containing polyester fibers was laminated and dried and cured at 130 캜 for 50 seconds to prepare a radiation-shielding textile composite.
Example 4
10 parts by weight of a medium density polyethylene powder, 5 parts by weight of a low density polyethylene powder and 5 parts by weight of a high density polyether powder were mixed with 100 parts by weight of an acrylic resin (manufactured by Kagaku Kagaku Co., Ltd.).
Then, 20 parts by weight of polyether ether ketone was mixed with 100 parts by weight of the acrylic resin, and 10 parts by weight of methyl ethyl ketone (MEK) and 15 parts by weight of toluene were added to 100 parts by weight of the acrylic resin. To prepare a first preliminary composition.
10 parts by weight of molybdenum powder, 5 parts by weight of tantalum powder, 40 parts by weight of tungsten oxide (WO 3 ) powder as a metal oxide powder and 20 parts by weight of barium sulfate (BaSO 4 ) as an inorganic additive were added to the primary preliminary composition And premixed.
Then, 15 parts by weight of paraffin, 12 parts by weight of boron carbide (B 4 C), and 7 parts by weight of the same nano carbon fiber as that of Example 1 were added and mixed with 100 parts by weight of the acrylic resin to prepare a solution containing the radiation shielding composition Respectively.
A radiation shielding film was prepared by coating a solution containing the composition for radiation shielding on a Release Paper with a dam coater so as to have a thickness of 80 mu m. Then, 100 parts by weight of a polyurethane adhesive resin, 10 parts by weight of a curing agent, 20 parts by weight of DMF and 20 parts by weight of MEK were mixed to prepare an adhesive, and the adhesive was applied to a thickness of 300 mu m using a comma knife. A fabric containing polyester fibers was laminated on the adhesive and dried and cured at 130 캜 for 50 seconds to prepare a radiation-shielding textile composite.
Comparative Example 1
A textile composite for radiation shielding was prepared in the same manner and under the same conditions as in Example 1, except that the polyurethane resin was used alone instead of the primary preliminary resin composition.
Comparative Example 2
A textile composite for radiation shielding was prepared according to the same method and conditions as in Example 1 except that paraffin and nano carbon powder were not used.
Comparative Example 3
4 parts by weight of molybdenum powder as a metal powder, 3 parts by weight of tantalum powder, 35 parts by weight of tungsten oxide (WO 3 ) powder as a metal oxide powder and 5 parts by weight of barium sulfate (BaSO 4 ) A textile composite for radiation shielding was prepared in the same manner and under the same conditions as in Example 1 except that only 35 parts by weight of tungsten was used alone.
[Test Example]
Test Example 1: Evaluation of radiation shielding performance
The radiation shielding experiments were carried out in a linear accelerator laboratory for the radiation-shielding textile composites prepared according to Examples 1 to 4 and Comparative Examples 1 to 3.
Specifically, the radiation-shielding textile composite prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was cut into 50 × 50 cm, and then the radiation shielding ratio was calculated according to the average energy and the source shown in Tables 1 and 2 After 10 measurements with different positions each time, the average value and the variation rate were measured and shown in the following Tables 1 and 2. The meaning of the change rate is as shown in Equation 3 shown below.
&Quot; (3) "
(%) = Measured maximum radiation shielding rate - measured minimum radiation shielding rate
According to Tables 1 and 2, the shielding ratio of the radiation shielding fibers according to Comparative Examples 1 to 3 was lower than that of the textile composite for radiation shielding according to Examples 1 to 4, except for the alpha rays, Respectively. Therefore, it can be seen that the radiation-shielding textile composite according to Examples 1 to 4 of the present invention has excellent shielding effect on radiation of beta rays, gamma rays, and x-rays.
Test Example 2: Evaluation of Neutron Shielding Performance
The neutron shielding performance of the radiation-shielding textile composite prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated and shown in Table 3 below.
A Neutron Beam Exit with a Constant Size and Measure the Neutron Intensity The detector is placed at a certain distance (5 cm) from the exit, and the ratio of the number of neutrons incident and the neutron volume passed through the radiation shielding textile composite is used to calculate the thermal neutron absorption Sectional area coefficient.
The calculation method of the neutron absorption cross-sectional area coefficient is shown in Equation 2 below.
&Quot; (4) "
I / I 0 = L-μ or μ = [log (I 0 / I)]
(I 0 : incident beam, I: transmitted beam, L: scattering cross sectional area coefficient, and μ: absorption sectional area coefficient)
μ (cm -1 )
According to Table 3, when the polyethylene resin (neutron shielding resin) is not used as in Comparative Example 1, the neutron shielding effect is reduced by about 20%. Also, as in Comparative Example 2, when the neutron shielding material is used as a single material, that is, only the boron compound is used and the paraffin and the carbon nano powder are not used, the radiation shielding effect is reduced by about 10%. Accordingly, it was confirmed that the radiation-shielding textile composites of Examples 1 to 4 including polyethylene resin and using paraffin, boron compound, and carbon nano powder together as a neutron shielding material had excellent shielding effect even for neutrons.
Example 5 and Comparative Example 4
15 parts by weight of polyether ether ketone (PEEK) resin (Example 5) and 15 parts by weight of polyether ketone (PEK) (Comparative Example 4) were added to 100 parts by weight of polyurethane resin, Radiation shielding sheets (25 cm in width and 20 cm in height) were irradiated with 10 Gy radiation at room temperature for 12hr, 24hr, 48hr and 96hr. Tensile strength reduction test, tear strength reduction test, χ ray shielding test, γ ray shielding test were performed.
Tensile strength and tear strength were evaluated by the K SK 0521 test method. The χ ray shielding test conditions were 100 Kvp, 400 mA, 0.1 sec, and the dose (l0) incident on the sample and the dose (lt) were measured by each dosimeter and calculated by the shielding equation.
Shielding ratio (%) = ((lo-lt) / lo) x100
The γ-ray was also evaluated by comparing gamma-ray counts with and without samples between the high-purity Ge-detector and the gamma-dotted circle.
Table 4 shows the tensile strength test according to the irradiation time of the tensile strength (K SK 0521 standard) of Example 5 and Comparative Example 4. Table 5 shows the strength reduction test according to the irradiation time of the tear strength (K SK 0521 standard) of Example 5 and Comparative Example 4. Table 6 shows the X-ray shielding test of Example 5 and Comparative Example 4. Table 7 shows the gamma ray shielding test of Example 5 and Comparative Example 4.
Investigation time
The tensile strength
(PEK)
The tensile strength
(%)
Phosphorus strength
(PEK)
Phosphorus strength
(%)
Investigation time
χ line shielding rate
(PEK)
χ line shielding rate
(%)
Investigation time
γ ray shielding rate
(PEK)
γ ray shielding rate
(%)
Referring to Tables 4 to 7, it can be seen that Example 5 (polyether ether ketone (PEEK)) has the same tensile strength and tear strength as Comparative Example 4 (polyether ketone (PEK) In the case of Comparative Example 5, the decrease rate of the strength was sharply increased as the spinning time was longer, but the decrease in the strength was relatively slow in Example 5. Further, in Comparative Example 5, The lowering rate of the gamma ray shielding is 10 times or more lower than that of Example 4, so that the shielding ability can be maintained even when exposed to long-term radiation.
Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (24)
A neutron shielding material comprising at least one selected from the group consisting of water capsules, polyvinyl alcohol (PVA), medium density polyethylene (MDPE), high density polyethylene (HDPE), and low density polyethylene (LDPE);
Polyetheretherketone (PEEK) for improved durability and
A composition for shielding radiation, comprising at least two additive materials selected from the group consisting of metal powder, metal oxide powder, paraffin, boron compound and carbon powder.
5 to 30 parts by weight of the neutron shielding material, 5 to 30 parts by weight of the polyether ether ketone (PEEK), and 1 to 80 parts by weight of the additive material.
Adding a solvent to the composition to adjust dispersion and viscosity of the composition;
Adding at least one additive selected from the group consisting of metal powder, metal oxide powder, paraffin, boron compound, carbon powder and nano-sized clay to the composition; And
And coating the composition with the composition.
19. A radiation shielding textile composite according to claim 19 formed on said textile.
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