CN113462039A - Preparation method and product of bismuth-based radiation shielding flexible protective material - Google Patents
Preparation method and product of bismuth-based radiation shielding flexible protective material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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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
- C08K2003/0837—Bismuth
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Abstract
The invention relates to a preparation method of a bismuth-based radiation shielding flexible protective material and a product thereof, wherein functional shielding powder is added into a rubber-based high molecular polymer to form a shielding colloid body through mixing and refining, and after molding and curing (or vulcanization), the radiation shielding flexible protective material or the product with certain radiation shielding efficiency, certain strength and certain shape is obtained. The application has the obvious characteristics of safe and nontoxic products, high shielding efficiency, simple and controllable process flow, wide material source and easy stable mass production.
Description
Technical Field
The application relates to a manufacturing method and a product of a radiation shielding and protecting material for X rays and gamma rays, in particular to a preparation method and a product of a bismuth-based radiation shielding flexible protecting material, belonging to the field of preparation of functional materials.
Background
At present, the flexible protective material for shielding X-ray and gamma-ray radiation at home and abroad is mainly lead rubber or other lead-containing materials. Because of the toxicity of lead and the outstanding environmental protection problem, people are researching and searching lead-free nontoxic flexible protective materials for shielding and protecting X-ray and gamma-ray radiation.
CN110105743A patent application discloses a lead-free X, gamma ray radiation shielding protective material and its preparation method. Uniformly mixing erbium-source solid powder, tungsten-source solid powder, bismuth-source solid powder and a coupling agent to obtain a first mixture; adding a polyurethane emulsion into the first mixture and mixing to prepare a second mixture; and curing the second mixture to obtain the X-ray and gamma-ray radiation shielding and protecting material. The lead-free X-ray and gamma-ray radiation shielding and protecting material provided by the invention takes an erbium source, a tungsten source and a bismuth source as ray shields, fully utilizes the complementary effect of absorption boundaries of K layers of Er, W and Bi and realizes effective shielding of X-rays and gamma-rays. However, the erbium source and the tungsten source used in this patent application are both very expensive materials.
CN110828019A discloses a silica gel-based flexible shielding material for gamma ray shielding and a preparation method thereof, the material is prepared from silica gel A, silica gel B and tungsten powder, and the preparation comprises the following steps: 1) weighing silica gel A, silica gel B and tungsten powder, and mixing and stirring the silica gel A and the silica gel B uniformly to obtain a mixture; 2) grinding tungsten powder, pouring the ground tungsten powder into the mixture obtained in the step 1), and uniformly stirring to obtain a mixture of silica gel and tungsten powder; 3) and pouring the mixture of the silica gel and the tungsten powder into a mold, then placing the mold in a vacuum tank, vacuumizing the vacuum tank, and cooling the mold after bubbles disappear to obtain the silica gel-based flexible shielding material for gamma ray shielding. Tungsten is a rare strategic resource managed and controlled by the state; due to restrictions of policy, economy and the like, the patented technology has no general applicability.
CN1314052C relates to a rare earth modified lead-free X-ray shielding rubber. One part of inorganic rare earth is subjected to surface modification treatment, the other part of inorganic rare earth is subjected to organic reaction treatment to prepare organic rare earth salt, and the organic rare earth salt and the rubber are added into rubber in a matching way according to a certain proportion, so that the modified lead-free X-ray shielding rubber is obtained, and the shielding property and the mechanical property of the material can achieve ideal effects. Can be widely used for the protection of medical diagnosis X-ray machines, X-ray diffractometers, emitters of electron microscopes and other workers in occasions accompanied with X-ray generation.
In order to overcome the problems of high cost, difficult forming, low strength, easy deformation, difficult mass production and the like of the traditional lead-free X-ray and gamma-ray radiation shielding protective material, the invention adopts functional shielding powder as a shielding material and high polymer material as a carrier to optimize a formula and a forming process, invents a novel lead-free X-ray and gamma-ray radiation shielding flexible protective material, namely a bismuth-based radiation shielding flexible protective material, and is particularly suitable for the production of shielding clothes and the radiation shielding protection of fixed or moving positions.
The application has the obvious characteristics of safe and nontoxic products, high shielding efficiency, simple and controllable preparation process flow, wide material source and easy stable mass production.
Disclosure of Invention
The lead-free X-ray and gamma-ray radiation shielding protective material is a radiation shielding flexible protective material or a product with certain radiation shielding efficiency, certain strength and certain shape, which is obtained by adding functional shielding powder into a rubber-based high molecular polymer, mixing and refining to form a shielding colloid body, and molding and curing (or vulcanizing).
The technical scheme of the application is as follows:
the radiation shielding flexible protective material or product is formed by molding and vulcanizing a shielding rubber material body (for convenience, the specific rubber is cured and is hereinafter referred to as vulcanization). The shielding colloid body is prepared by mixing and refining functional shielding powder, rubber-based high molecular polymer and other additives. The functional shielding powder is formed by mixing bismuth-based shielding powder with other shielding powder. The rubber-based high molecular polymer is natural rubber, ethylene propylene rubber, polyurethane, silica gel or other rubber. Other additives include a curing agent, a modifier, a reinforcing agent (reinforced with plant fibers, carbon fibers, glass fibers, etc., if necessary), and the like.
The preparation method comprises mixing functional shielding powder, rubber-based high molecular polymer and other additives in rubber internal mixer, open mill or other rubber mixing equipment to obtain shielding rubber material, and molding and vulcanizing the rubber material in mold cavity or vulcanizing tank; or after the rubber material is pressed and rolled, the rubber material is continuously vulcanized and discharged through a drum type vulcanizing machine. And after the vulcanization is finished, obtaining the bismuth-based radiation shielding flexible protective material or product.
The production process flow is shown in figure 1.
The functional shielding powder plays a role in shielding and protecting X-ray and gamma-ray radiation, and is formed by mixing powder consisting of bismuth-based shielding powder and other shielding element powder (the other shielding element powder is a non-lead powder material such as tantalum, niobium, tungsten, tin, antimony, barium and the like), wherein the mass percentage of the bismuth-based shielding powder is 70-100%, and the balance is other element shielding powder.
The bismuth-based shielding powder is prepared by mixing metal bismuth powder and bismuth oxides with different crystal forms: the fineness of the metal bismuth powder is-100 meshes or more and 95 percent to-200 meshes or more and 95 percent, the mass percentage of the metal bismuth powder in the bismuth-based shielding powder is 0 to 100 percent (the preferred proportion is 20 to 80 percent), and the rest is bismuth oxide powder with different crystal forms. The bismuth oxide powder is prepared from beta-Bi2O3Powder and alpha-Bi2O3Mixing the powder: beta-Bi2O3And alpha-Bi2O3The average grain diameter of the powder is 1-5 microns and 2-80 microns respectively, beta-Bi2O3The weight percentage of the bismuth oxide powder is 0-100% (the preferred proportion is 25% -75%), and the rest is alpha-Bi2O3And (3) powder.
When the requirement of shielding effectiveness is relatively low, such as the requirement of weight, volume and strength is not strict, the shielding powder of other elements can be formed by mixing cheap powders such as antimony powder, antimony oxide powder, barium sulfate and the like. When the shielding effectiveness is required to be high, such as strict requirements on weight, volume and strength, the shielding powder of other elements can be tantalum powder, niobium powder, tungsten powder, tin powder or their oxide powder, or the powder of these metals or their oxides is mixed according to a certain proportion.
The mass ratio principle of the rubber-based high molecular polymer to the functional shielding powder is as follows: according to the application and the technical characteristics of the shielding material, the shielding material is reasonably proportioned according to the principle that the softness and the tear resistance are high, the shielding effectiveness is satisfied, and the weight is light. The mass ratio of the rubber-based high molecular polymer to the functional shielding powder is 1:1-10 (the preferable ratio is 1: 3-6), namely: 1 part of rubber-based high molecular polymer and 1-10 parts (the preferred proportion is 3-6) of functional shielding powder.
The shielding colloid body is prepared by mixing and refining functional shielding powder, rubber-based high-molecular polymer, curing agent, modifier and reinforcing agent. The functional shielding powder and the rubber-based high molecular polymer can be mixed and refined together with other additives when the functional shielding powder and the rubber-based high molecular polymer are mixed and refined in an internal mixer or an open mill, or all or part of other additives can be added after the rubber-based high molecular polymer and the functional shielding powder are refined, or the functional shielding powder and other additives can be gradually added in the refining process. The rubber-based high polymer, the functional shielding powder, the curing agent, the modifier and the reinforcing agent are sequentially added, and the respective addition amount is combined correspondingly according to different rubber types and use requirements.
The shielding material is obtained by vulcanizing the shielding rubber body on a universal or special vulcanizing machine. The general vulcanizing machine generally uses a flat vulcanizing machine and is matched with a special mould to produce shielding cut pieces. The special vulcanizer is a calender and drum vulcanizer production line specially designed to produce the shielding plate. The molded shielding rubber body can also be placed into a vulcanizing tank for vulcanization. The vulcanization temperature is generally 50-180 ℃, and the vulcanization time is generally 5-120 min.
The radiation shielding and protecting material can be made into radiation shielding and protecting clothing finished products, cutting pieces for protection, shielding and protecting plates, single-side or double-side composite cloth (or composite fiber fabrics made of specified materials), radiation shielding and protecting plates with middle fiber reinforced layers, and other radiation shielding and protecting materials with special requirements on special shapes.
The radiation shielding cut-parts goods of this application has avoided the consume of material through special design and mould shaping, can reduce the cost by a wide margin.
Detailed description of the preferred embodiments
The following examples further illustrate the implementation of the technical solutions of the present application.
Examples
Example 1
100g of natural rubber, and 10 additives are added; 500g of bismuth oxide (. beta. -Bi having an average particle diameter of 1.5 μm)2O3300g of powder; alpha-Bi having an average particle diameter of 5 μm2O3200g of powder), mixing and refining, pressing the powder on a calender to form a shielding rubber body with the thickness of 1.6mm, and then pressing and forming the rubber body on a flat vulcanizing machine, wherein the vulcanizing temperature is 150 ℃, and the vulcanizing time is 8 min. After demoulding, X-ray and gamma-ray radiation shielding flexible protective clothing pieces with shielding effectiveness equivalent to 0.50mm lead equivalent are obtained. A photograph of the shielding protective clothing made of the cut pieces is shown in figure 2.
Example 2
100g of ethylene propylene rubber, and 8g of additive is added; 100g of-200 mesh metallic bismuth powder and 200g of bismuth oxide (wherein: beta-Bi having an average particle diameter of 2 μm2O3100g of powder; alpha-Bi having an average particle diameter of 15 μm2O3100g of powder and 70 g of 325-mesh barium sulfate, and the shielding rubber body is prepared by mixing, refining and compression molding, and is compression molded by a special mold on a flat vulcanizing machine. The vulcanizing temperature is 140 ℃, the vulcanizing time is 12 min, and the X-ray and gamma-ray radiation shielding protective plate with the thickness of 1.2mm and the shielding effectiveness equivalent to 0.35mm lead equivalent is obtained after demoulding.
Example 3
100g of polyurethane rubber, and 8g of additive is added; 100g of-200 mesh metallic bismuth powder and 200g of bismuth oxide (wherein: beta-Bi having an average particle diameter of 1.5 μm)2O3100g of powder; alpha-Bi having an average particle diameter of 43 μm2O3100g of powder, 50g of tantalum oxide with 200 meshes, mixing and refining, arranging a calender roll on a calender, pressing the mixture at 50 ℃ to form a shielding rubber body with the thickness of 1.0mm, and continuously forming the rubber body on a drum vulcanizer, wherein the vulcanization temperature is 130 ℃, and the vulcanization time is 15 min, so that the X-ray and gamma-ray radiation shielding flexible protection plate with the shielding effectiveness equivalent to 0.25mm lead equivalent is obtained.
Example 4
100g of modified liquid silica gel and 5g of additive; 300g of bismuth oxide (wherein: beta-Bi having an average particle diameter of 1.5 μm)2O3100g of powder; alpha-Bi having an average particle diameter of 75 μm2O3200g of powder), refining the powder into a shielding colloid body in a vacuum mixer at normal temperature, pressing the colloid body into a roller type calender with double-sided paved fiber fabrics (cloth) by a colloid pressing device, heating to 160 ℃, and continuously obtaining the X-ray and gamma-ray radiation shielding protective soft composite sectional material with double-sided paved fabric and radiation shielding effectiveness equivalent to 0.175mm lead equivalent when the colloid layer is 0.8 mm.
Claims (4)
1. A bismuth-based radiation shielding flexible protective material and a preparation method thereof are disclosed, wherein the bismuth-based radiation shielding flexible protective material is formed by molding and vulcanizing (or curing) a shielding rubber material body; the shielding colloid body is prepared by mixing and refining functional shielding powder, rubber-based high molecular polymer and other additives; it is characterized in that: the functional shielding powder is formed by mixing bismuth-based shielding powder with other shielding powder; the rubber-based high molecular polymer is natural rubber, ethylene propylene rubber, polyurethane, silica gel or other rubber; the preparation method comprises mixing functional shielding powder, rubber-based high molecular polymer, and other additives in rubber internal mixer, open mill or other rubber mixing equipment to obtain shielding rubber material, and molding and vulcanizing the rubber material in mold cavity or vulcanizing tank; or after the rubber material is rolled, continuously vulcanizing the rubber material by a drum vulcanizer; after vulcanization, the bismuth-based radiation shielding flexible protective material or product is obtained.
2. The preparation method of the bismuth-based radiation shielding flexible protective material and the product thereof according to claim 1 are characterized in that: the mass percentage of the bismuth-based shielding powder is 70-100%, and the rest is other element shielding powder; the bismuth-based shielding powder is prepared by mixing metal bismuth powder and bismuth oxides with different crystal forms: the fineness of the metal bismuth powder is-100 meshes or more and 95 percent to-200 meshes or more and 95 percent, the mass percentage of the metal bismuth powder in the bismuth-based shielding powder is 0-100 percent (the preferred proportion is 20-80 percent), and the rest is bismuth oxide powder with different crystal forms; the bismuth oxide powder is prepared from beta-Bi2O3Powder and alpha-Bi2O3Mixing the powder: beta-Bi2O3And alpha-Bi2O3The average grain diameter of the powder is 1-5 microns and 2-80 microns respectively, beta-Bi2O3The weight percentage of the bismuth oxide powder is 0-100% (the preferred proportion is 25% -75%), and the rest is alpha-Bi2O3And (3) powder.
3. The preparation method and the product of the bismuth-based radiation shielding flexible protective material according to the claims 1 and 2 are characterized in that: the shielding colloid body is prepared by mixing and refining functional shielding powder, rubber-based high-molecular polymer, curing agent, modifier and reinforcing agent; the mass ratio of the rubber-based high molecular polymer to the functional powder is 1:1-10 (the preferable ratio is 1: 3-6).
4. A method for preparing a bismuth-based radiation shielding flexible protective material and a product thereof according to the claims 1, 2 and 3, wherein: the shielding material is obtained by vulcanizing (or curing) a shielding rubber body on a general or special vulcanizing (curing) machine; the vulcanization temperature is generally 50-180 ℃, and the vulcanization time is generally 5-120 min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975310A (en) * | 2023-01-17 | 2023-04-18 | 长沙原子高科医药有限公司 | Flexible protective material and preparation method and application thereof |
| CN115975310B (en) * | 2023-01-17 | 2024-04-26 | 长沙原子高科医药有限公司 | Flexible protective material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003130990A (en) * | 2001-10-25 | 2003-05-08 | Fujix:Kk | Radiation shield material and its production method |
| WO2005049713A1 (en) * | 2003-11-18 | 2005-06-02 | Arntz Beteiligungs Gmbh & Co. Kg | Radiation shielding material for protective clothing, such as aprons or the like |
| CN112867542A (en) * | 2018-10-01 | 2021-05-28 | 比奥尼克莱公司 | Topical photon barriers comprising bismuth oxide colloids |
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2021
- 2021-08-10 CN CN202110905753.7A patent/CN113462039B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003130990A (en) * | 2001-10-25 | 2003-05-08 | Fujix:Kk | Radiation shield material and its production method |
| WO2005049713A1 (en) * | 2003-11-18 | 2005-06-02 | Arntz Beteiligungs Gmbh & Co. Kg | Radiation shielding material for protective clothing, such as aprons or the like |
| CN112867542A (en) * | 2018-10-01 | 2021-05-28 | 比奥尼克莱公司 | Topical photon barriers comprising bismuth oxide colloids |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975310A (en) * | 2023-01-17 | 2023-04-18 | 长沙原子高科医药有限公司 | Flexible protective material and preparation method and application thereof |
| CN115975310B (en) * | 2023-01-17 | 2024-04-26 | 长沙原子高科医药有限公司 | Flexible protective material and preparation method and application thereof |
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