Gamma ray flexible shielding material and method of making same

Abstract

The present application provides a kind of gamma ray flexible shielding material, including fiber cloth matrix and high phenyl silica gel and protective body coated on fiber cloth matrix;Protective body includes lanthanide series element, transition element or main group metal single element powder, or its oxide, carbide, nitride powder, or its sulfate, carbonate;Increase the biocompatibility with fiber cloth matrix, better adhere to the surface of fiber cloth matrix, not only increase the shielding effect of material, and the protective body coating of layered structure has good thermal stability and mechanical properties, flexibility is greatly improved;Also provide the preparation method of the above material, high phenyl silica gel and protective body are coated in multiple times, and after each time of glue is adhered, vacuum laminating is carried out immediately, to remove the air or bubble between glue and fiber cloth matrix and between multiple layers of glue;And can improve the compatibility between glue, more easily bonded firmly.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flexible materials, in particular to a gamma ray flexible shielding material and a preparation method thereof. BACKGROUND

[0002] In the scene of nuclear power plants, ionizing radiation poses a significant threat to human health, therefore, radiation protection is essential. Traditional radiation protection materials are mainly divided into two categories, one is metal-based protection material, represented by lead plate, which has good protection ability, but poor portability, and is suitable for fixed occasions; the other is heavy metal composite material, mainly lead-based composite material, such as lead rubber, lead glass, which partially realizes flexibility and transparency, but still has great deficiencies, one is that lead has biological toxicity, poor stability, easy to volatilize, affecting the nervous system and its biological tissue organs,

[0003] In the prior art, in the scene of nuclear power plants, lead plates are generally used for primary circuit protection, and workers must wear lead clothes for gamma ray protection. In addition, key nuclear facilities and strategic equipment also need to be protected from gamma rays. However, existing gamma ray protection materials are not flexible, and the restrictions on wearing are relatively large. Therefore, the research of flexible gamma ray shielding materials is imperative. SUMMARY

[0004] The first object of the present application is to provide a gamma ray flexible shielding material, comprising a fiber cloth substrate and high phenyl silica gel and a protection body coated on the fiber cloth substrate; the protection body comprises lanthanide element, transition element or main group metal single element powder, or oxide, carbide, nitride powder thereof, or sulfate, carbonate thereof; specifically, it can be: bismuth oxide, tin oxide, lanthanum oxide, samarium oxide, gadolinium oxide, erbium oxide, ytterbium oxide, hafnium oxide, tantalum oxide, tungsten trioxide, tin trioxide and their single metal powders, such as tungsten powder, bismuth, tin powder, and their sulfates, carbonates and the like; the mass of the high phenyl silica gel accounts for 10-30% of the mass of the high silica fiber cloth, and the mass of the protection body accounts for 30-50% of the mass of the high silica fiber cloth.

[0005] The second object of the present application is to provide a preparation method of the above-mentioned gamma ray flexible shielding material, comprising the following steps:

[0006] S1. Mix part of the protection body with part of the high phenyl silica gel uniformly, coat on the inner and outer surfaces of the fiber cloth substrate, perform first vacuum bonding, and add vulcanizing agent at the same time to obtain a first fiber cloth substrate;

[0007] S2. Continue to spray part of the high phenyl silica gel on the outer surface of the first fiber cloth substrate, perform second vacuum bonding, and add vulcanizing agent at the same time to obtain a second fiber cloth substrate;

[0008] S3. The remaining protective body is mixed with part of the high-phenyl silica gel, and then sprayed on the outer surface of the second fiber cloth substrate to perform a third vacuum bonding, and a vulcanizing agent is added to obtain a third fiber cloth substrate, and finally, high-temperature tunnel kiln fluidization forming is performed to obtain the shielding material.

[0009] The technical scheme of the embodiment of the application has at least the following advantages and beneficial effects:

[0010] 1. The shielding material uses the coordination cross-linking of carboxylate ions in sodium alginate and lanthanide elements, transition elements or main group metal ions, and introduces polymethyl methacrylate for physical doping, so that a protective body shielding material with a layered structure is finally obtained, the biocompatibility with the fiber cloth substrate is increased, and the protective body is better attached to the surface of the fiber cloth substrate, which not only increases the shielding effect of the material, but also improves the thermal stability and mechanical properties of the protective body coating with a layered structure, and greatly improves the flexibility.

[0011] 2. The preparation method coats the high-phenyl silica gel and the protective body in multiple times, and performs vacuum bonding after each time of coating to remove air or bubbles between the glue and the fiber cloth substrate and between the multiple layers of glue, so that the compatibility between the glues is improved, and the glues are more easily and firmly bonded. DETAILED DESCRIPTION

[0012] To make the purpose, technical scheme and advantages of the embodiments of the application clearer, the technical scheme in the embodiments of the application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0013] A gamma-ray flexible shielding material and a preparation method thereof provided by the embodiments of the application will be specifically described below.

[0014] A gamma-ray flexible shielding material, comprising a fiber cloth substrate, high-phenyl silica gel and a protective body coated on the fiber cloth substrate, wherein the mass of the high-phenyl silica gel accounts for 10-30% of the mass of the high-silica fiber cloth, and the mass of the protective body accounts for 30-50% of the mass of the high-silica fiber cloth.

[0015] The protective body comprises one or more combinations of lanthanide elements, transition elements or main group metal single element powders, or oxide, carbide, nitride powders thereof, or sulfate, carbonate thereof; further comprising modified chitosan in equal mass ratio, the modified chitosan is modified by sodium alginate and polymethyl methacrylate; the mass ratio of chitosan, sodium alginate and polymethyl methacrylate is 5-10:2-5:1; specifically, the preparation of the modified chitosan is as follows: butanedioic anhydride is added to a sodium alginate solution, then a chitosan solution is added, after a period of reaction, polymethyl methacrylate is added and mixed, after a period of time, vacuum drying treatment is performed, and the modified chitosan is obtained.

[0016] The carboxylate ions in the sodium alginate and the lanthanide element, transition element or main group metal ions can be coordinated and crosslinked, and at the same time, polymethyl methacrylate is introduced for physical doping, so that the protective body shielding material with a layered structure is finally obtained, the biocompatibility with the fiber cloth matrix is increased, and the fiber cloth matrix surface is better attached, not only the shielding effect of the material is increased, but also the layered protective body coating has good thermal stability and mechanical properties, and the flexibility is greatly improved.

[0017] Further, the fiber cloth matrix includes but is not limited to any one of high-silicon fiber cloth, ceramic fiber cloth, basalt fiber cloth, carbon fiber cloth, silica fiber cloth, aluminum foil fiber cloth, alumina fiber cloth and zirconia fiber cloth.

[0018] The preparation method of the above gamma ray flexible shielding material comprises the following steps:

[0019] S1. Part of the protective body is uniformly mixed with part of high-phenyl silica gel, and is coated on the inner and outer surfaces of the fiber cloth matrix to perform first vacuum bonding, and a vulcanizing agent is added to obtain a first fiber cloth matrix;

[0020] S2. Part of the high-phenyl silica gel is continuously sprayed on the outer surface of the first fiber cloth matrix to perform second vacuum bonding, and a vulcanizing agent is added to obtain a second fiber cloth matrix;

[0021] S3. The remaining protective body is uniformly mixed with part of high-phenyl silica gel, and is continuously sprayed on the outer surface of the second fiber cloth matrix to perform third vacuum bonding, and a vulcanizing agent is added to obtain a third fiber cloth matrix, and finally high-temperature tunnel kiln fluidization forming is performed to obtain the shielding material.

[0022] The high-phenyl silica gel is coated in multiple times in the present application, and vacuum bonding is performed immediately after each time of glue sticking to remove air or bubbles between the glue and the fiber cloth matrix and between the multiple layers of glue;

[0023] More importantly, only a small part of the adhesive is applied first in the first coating, and the adhesive and the substrate are bonded with a protective body, creating a stable adhesive bond. Then, based on this, only the adhesive is applied, which not only has good compatibility with the aforementioned adhesive and is easy to bond firmly, but also provides a connection bridge for the subsequent adhesive and protective body adhesion. Most of the protective body is coated on the outer layer as a shielding layer, and due to the coating of the adhesive and the compatibility between the outer protective body and the inner protective body, the coating effect of the multi-layer coating is more stable, and better shielding effect can be achieved. Compared to the one-time coating of high phenyl silicone and protective body on the fiber cloth substrate and then vacuum bonding, the bonding is more uniform, the adhesion is better, and the air is more thoroughly removed, avoiding the phenomenon of air bubbles between high phenyl silicone and protective body or inside high phenyl silicone and protective body.

[0024] Further, the mass ratio of the amount of high phenyl silicone added in S1, the amount of high phenyl silicone added in S2, and the amount of high phenyl silicone added in S3 is 1:3-5:1-2.

[0025] Further, in S1, the mass ratio of the protective body to high phenyl silicone is 1:1-3; in S3, the mass ratio of the protective body to high phenyl silicone is 3-5:1.

[0026] Further, in each step, the mass ratio of the amount of vulcanizing agent added to the amount of high phenyl silicone is 1:1-3.

[0027] Further, the first vacuum bonding includes: sequentially performing preheating, bonding and cooling; the temperature during preheating is 90-130℃, the preheating time is 10-30min; the temperature during bonding is 130-170℃, the bonding time is 10-30min, the pressure is 5-10Mpa, and the temperature during cooling is 50-60℃, the cooling time is 20-30min; thereby removing air or bubbles between high phenyl silicone and protective body and the fiber cloth substrate, and allowing a small amount of high phenyl silicone to quickly bond firmly with the fiber cloth substrate, reducing the possibility of air bubble generation.

[0028] Further, the second vacuum bonding includes: sequentially performing preheating, bonding and cooling; the temperature during preheating is 110-150℃, the preheating time is 10-30min; the temperature during bonding is 150-210℃, the bonding time is 10-30min, the pressure is 10-30Mpa; thereby removing air or bubbles between high phenyl silicone and the aforementioned high phenyl silicone coating, and possibly remaining bubbles in the previous step, and the compatibility between the coating layers is better, which can be better bonded.

[0029] Further, the third vacuum bonding comprises: sequentially performing preheating, bonding and cooling; the temperature during preheating is 150-180℃, and the preheating time is 10-30min; the temperature during bonding is 180-250℃, the bonding time is 10-30min, and the pressure is 30-60Mp; so that the air or bubbles between the coating layers and the bubbles possibly remaining in the previous step are removed, and the coating layers are uniformly distributed and have good adhesion.

[0030] Embodiment 1

[0031] A gamma ray flexible shielding material comprises a fiber cloth substrate and high-phenyl silica gel and a protective body coated on the fiber cloth substrate; the mass of the high-phenyl silica gel accounts for 20% of the mass of the high-silica fiber cloth, and the mass of the protective body accounts for 40% of the mass of the high-silica fiber cloth.

[0032] The protective body comprises tungsten oxide, bismuth oxide and modified chitosan in equal mass ratios, wherein the modified chitosan is prepared by adding succinic anhydride into a sodium alginate solution, then adding a chitosan solution, reacting for 2h, then adding polymethyl methacrylate and uniformly mixing, and after 1h, vacuum drying treatment to obtain the modified chitosan; wherein the mass ratio of chitosan, sodium alginate, polymethyl methacrylate and succinic anhydride is 10:5:1:1.

[0033] The preparation method of the above-mentioned gamma ray flexible shielding material comprises the following steps:

[0034] S1. The protective body and the high-phenyl silica gel are uniformly mixed in a mass ratio of 1:1, coated on the inner and outer surfaces of the high-silica fiber cloth, and subjected to first vacuum bonding while adding sulfur to obtain a first fiber cloth substrate; wherein the total mass of the mixed coating layer accounts for 5% of the mass of the high-silica fiber cloth; the first vacuum bonding comprises: sequentially performing preheating, bonding and cooling; the temperature during preheating is 100℃, and the preheating time is 10min; the temperature during bonding is 130℃, the bonding time is 10min, and the pressure is 5Mpa; and the temperature during cooling is 50℃, and the cooling time is 20min;

[0035] S2. Part of the high-phenyl silica gel is further sprayed on the outer surface of the first fiber cloth substrate, and second vacuum bonding is performed while adding sulfur to obtain a second fiber cloth substrate; the second vacuum bonding comprises: sequentially performing preheating, bonding and cooling; the temperature during preheating is 120℃, and the preheating time is 10min; the temperature during bonding is 150℃, the bonding time is 10min, and the pressure is 10Mpa;

[0036] S3. The remaining protective body is mixed with part of the high-phenyl silica gel, and is sprayed on the outer surface of the second fibrous cloth substrate to perform a third vacuum bonding, and sulfur is added to obtain a third fibrous cloth substrate. The third vacuum bonding comprises preheating, lamination and cooling in sequence. The preheating temperature is 150°C, and the preheating time is 10 min. The lamination temperature is 190°C, the lamination time is 10 min, and the pressure is 40 Mpa. Finally, high-temperature tunnel kiln fluidization forming is performed to obtain the shielding material.

[0037] Example 2

[0038] The difference between this example and Example 1 is that the mass of the high-phenyl silica gel accounts for 10% of the mass of the high-silica fibrous cloth, and the mass of the protective body accounts for 30% of the mass of the high-silica fibrous cloth. The protective body comprises bismuth oxide, tin oxide and modified chitosan.

[0039] Example 3

[0040] The difference between this example and Example 1 is that the mass of the high-phenyl silica gel accounts for 30% of the mass of the high-silica fibrous cloth, and the mass of the protective body accounts for 50% of the mass of the high-silica fibrous cloth. The protective body comprises bismuth oxide, gadolinium oxide and modified chitosan.

[0041] Example 4

[0042] The difference between this example and Example 1 is that the mass of the high-phenyl silica gel accounts for 20% of the mass of the high-silica fibrous cloth, and the mass of the protective body accounts for 30% of the mass of the high-silica fibrous cloth. The protective body comprises tungsten powder, samarium oxide and modified chitosan.

[0043] Example 5

[0044] The difference between this example and Example 1 is that the mass of the high-phenyl silica gel accounts for 20% of the mass of the high-silica fibrous cloth, and the mass of the protective body accounts for 30% of the mass of the high-silica fibrous cloth. The protective body comprises tin powder, ytterbium oxide and modified chitosan.

[0045] Example 6

[0046] The difference between this example and Example 1 is that the mass of the high-phenyl silica gel accounts for 20% of the mass of the high-silica fibrous cloth, and the mass of the protective body accounts for 30% of the mass of the high-silica fibrous cloth. The protective body comprises tungsten powder, gadolinium oxide and modified chitosan.

[0047] Comparative Example 1

[0048] The difference between this comparative example and Example 1 is that the chitosan is not modified.

[0049] Comparative Example 2

[0050] The difference between this comparative example and Example 1 is that the modified chitosan is not contained.

[0051] Comparative Example 3

[0052] The difference between the present comparative example and Example 1 is that the high-phenyl silica gel and the protective body are coated on the high-silica fiber cloth at one time in the preparation process, and then vacuum laminated.

[0053] Experimental Example

[0054] The gamma ray flexible shielding materials provided by Examples 1-4 and Comparative Examples 1-3 are respectively denoted as Experimental Groups 1-7; specifications: 1m*50m (width*length); thickness: 0.8mm;

[0055] 1. The radiation protection performance test is carried out according to GBZ / T 147-2002 "Determination of X-ray protection material attenuation performance", and the X-ray protection shielding detection is carried out using standard X-rays (120 kV, additional filter is 2.50 mm Al), and the results are shown in Table 1.

[0056] Table 1: Shielding detection results of each experimental group

[0057]

[0058] It can be seen that the lead equivalent value of the gamma ray flexible shielding material obtained by the present application reaches 1.5mm Pb, indicating that it has good shielding and protection effect on X-rays; while the comparative examples cannot achieve excellent protection effect.

[0059] 2. The shielding efficiency of Experimental Groups 1-7 is shown in Table 2

[0060] Table 2: Shielding efficiency results of each experimental group

[0061]

[0062] It can be seen that the protective body used in the present application uses lanthanide elements and modified chitosan as shielding materials, which can obtain good radiation protection performance; while the comparative examples cannot achieve good radiation protection performance.

[0063] The above is only a preferred embodiment of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A flexible gamma-ray shielding material, characterized in that, Includes a fiber cloth matrix and a high-phenyl silicone coating and a protective layer on the fiber cloth matrix; The protective body includes lanthanide elements, transition elements or main group metal elemental powders, or their oxides, carbides, nitrides, or their sulfates or carbonates; The high-phenyl silicone accounts for 10-30% of the mass of the fiber cloth matrix, and the protective body accounts for 30-50% of the mass of the fiber cloth matrix. The protective body also includes modified chitosan, which is modified by sodium alginate and polymethyl methacrylate; the mass ratio of chitosan, sodium alginate and polymethyl methacrylate is 5-10:2-5:

1. The modified chitosan was prepared by adding succinic anhydride to a sodium alginate solution, then adding a chitosan solution, reacting for a period of time, adding polymethyl methacrylate and mixing, and then vacuum drying to obtain the modified chitosan.

2. The flexible gamma-ray shielding material according to claim 1, characterized in that, The fiber cloth matrix includes, but is not limited to, any one of the following: high silica fiber cloth, ceramic fiber cloth, basalt fiber cloth, carbon fiber cloth, aluminum foil fiber cloth, alumina fiber cloth, and zirconium oxide fiber cloth.

3. A method for preparing a flexible gamma-ray shielding material according to claim 1 or 2, characterized in that, Includes the following steps: S1. Mix part of the protective body with part of the high-phenyl silicone evenly, coat it on the inner and outer surfaces of the fiber cloth matrix, perform the first vacuum bonding, and add a vulcanizing agent to obtain the first fiber cloth matrix; S2. Then, mix some high-phenyl silicone and spray it onto the outer surface of the first fiber cloth matrix for a second vacuum bonding. At the same time, add a vulcanizing agent to obtain the second fiber cloth matrix. S3. Mix the remaining protective material with some high-phenyl silicone evenly, and continue to spray it onto the outer surface of the second fiber cloth matrix for a third vacuum bonding. At the same time, add a vulcanizing agent to obtain the third fiber cloth matrix. Finally, fluidize it in a high-temperature tunnel kiln to obtain the shielding material.

4. The method for preparing the flexible gamma-ray shielding material according to claim 3, characterized in that, The mass ratio of the amounts of high-phenyl silica gel added in S1, S2, and S3 is 1:3-5:1-2.

5. The method for preparing the flexible gamma-ray shielding material according to claim 3, characterized in that, In S1, the mass ratio of the protective body to high-phenyl silica gel is 1:1-3; in S3, the mass ratio of the protective body to high-phenyl silica gel is 3-5:

1.

6. The method for preparing the flexible gamma-ray shielding material according to claim 3, characterized in that, The first vacuum bonding process includes: preheating, bonding, and cooling in sequence; the preheating temperature is 90-130℃ and the preheating time is 10-30 minutes; the bonding temperature is 130-170℃ and the bonding time is 10-30 minutes, with a pressure of 5-10 MPa; the cooling temperature is 50-60℃ and the cooling time is 20-30 minutes.

7. The method for preparing the flexible gamma-ray shielding material according to claim 3, characterized in that, The second vacuum bonding process includes: preheating, bonding, and cooling in sequence; the preheating temperature is 110-150℃ and the preheating time is 10-30 min; the bonding temperature is 150-210℃, the bonding time is 10-30 min, and the pressure is 10-30 MPa.

8. The method for preparing the flexible gamma-ray shielding material according to claim 3, characterized in that, The third vacuum bonding process includes: preheating, bonding, and cooling in sequence; the preheating temperature is 150-180℃ and the preheating time is 10-30 minutes; the bonding temperature is 180-250℃ and the bonding time is 10-30 minutes, with a pressure of 30-60 MPa.

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