Heavy atom flexible metal thin film material for nuclear radiation and nuclear-biochemical integrated protection and preparation method of heavy atom flexible metal thin film material

Abstract

The invention provides a heavy atom flexible metal thin film material for nuclear radiation and nuclear-biochemical integrated protection and a preparation method of the heavy atom flexible metal thin film material, and belongs to the technical field of protection materials. The preparation method of the heavy atom flexible metal thin film material comprises the steps that the functional layer is evenly laid between the surface layer 1 and the bottom layer 2, and then hot pressing is conducted; the functional layer is a compound formed by metal or metal and non-metal elements; or the functional layer is a net film which uniformly adsorbs metal or a compound formed by metal and non-metal elements; the metal is lead powder, tungsten powder, bismuth powder, tantalum powder, tin powder or rare earth elements; the non-metallic elements are oxygen, carbon, nitrogen, phosphorus, arsenic, sulfur, selenium and tellurium. According to the invention, the powder or the short fiber structure of the heavy atom metal material is compounded with the organic thin film or the net film for fitting, so that the metal thin film with nuclear radiation and nuclear-biochemical integrated protection capability is formed, and the problem that the heavy atom metal is difficult to form a film is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of protective materials, and particularly relates to a heavy atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection and a preparation method thereof. Background Art

[0002] For the protection against nuclear radiation, the most basic technical means is to utilize the photoelectric effect and Compton scattering occurring from the interaction between heavy atoms and high-energy photons, so that the energy of the high-energy photons is continuously attenuated to achieve less radiation damage to the human body. The so-called heavy atoms refer to the atoms corresponding to the elements with larger atomic numbers in the periodic table. These elements are usually in a metallic state and have a relatively large density and a relatively high melting point. For example, lead, tungsten, tantalum, bismuth, gadolinium and some other rare earth elements. It is precisely because of these characteristics of heavy atoms that they have good high-energy ray shielding performance. However, the relatively large density and relatively high melting point make it difficult to process these metallic elements into filaments or thin films, and then form fabrics to make protective clothing. This limits their application in the field of nuclear radiation protection. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a heavy atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection and a preparation method thereof.

[0004] To achieve the above purpose, the present invention provides the following technical solutions:

[0005] One technical solution of the present invention is a preparation method of a heavy atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection. The functional layer is evenly laid between the surface layer 1 and the bottom layer 2, and then hot-pressed;

[0006] The functional layer is a metal or a compound formed by a metal and a non-metal element;

[0007] Or, the functional layer is a mesh uniformly adsorbed with a metal or a compound formed by a metal and a non-metal element;

[0008] The metal is lead powder, tungsten powder, bismuth powder, tantalum powder, tin powder or rare earth elements;

[0009] The non-metal elements are oxygen, carbon, nitrogen, phosphorus, arsenic, sulfur, selenium or tellurium.

[0010] In a preferred embodiment of the present invention, the functional layer is a binary or ternary alloy formed between lead powder, tungsten powder, bismuth powder, tantalum powder, tin powder and rare earth elements.

[0011] In the present invention, the morphology of the metal powder can be regular spherical or short fiber rods, or can also be irregular particles. In the present invention, the short fiber structure of the metal is also applicable to the present invention.

[0012] In a preferred embodiment of the present invention, the rare earth element is cerium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

[0013] In a preferred embodiment of the present invention, when the functional layer is a metal or a compound formed by a metal and a non-metal element, the amount of the metal or the compound formed by the metal and the non-metal element is: 200 - 3500 g / m 2 (preferably 200 - 300 g / m 2 , 300 - 500 g / m 2 , 500 - 1000 g / m 2 , 1000 - 2000 g / m 2 or 2000 - 3500 g / m 2 );

[0014] When the functional layer is a mesh membrane uniformly adsorbing a metal or a compound formed by a metal and a non-metal element, the amount of the metal or the compound formed by the metal and the non-metal element is: 200 - 3500 g / m 2 (preferably 200 - 300 g / m 2 , 300 - 500 g / m 2 , 500 - 1000 g / m 2 , 1000 - 2000 g / m 2 or 2000 - 3500 g / m 2 ).

[0015] In a preferred embodiment of the present invention, the surface layer 1 and the bottom layer 2 are both thermoplastic materials, non-woven fabrics, polyester fabrics, nylon fabrics, back-adhesive non-woven fabrics, back-adhesive nylon fabrics or back-adhesive polyester fabrics;

[0016] When the surface layer 1 and the bottom layer 2 are both thermoplastic materials, the functional layer is a metal or a compound formed by a metal and a non-metal element; at this time, the surface layer 1 and the bottom layer 2 are respectively denoted as organic film 1 and organic film 2;

[0017] When the surface layer 1 and the bottom layer 2 are both non-woven fabrics, polyester fabrics, nylon fabrics, back-adhesive non-woven fabrics, back-adhesive nylon fabrics or back-adhesive polyester fabrics, the functional layer is a mesh membrane uniformly adsorbing a metal or a compound formed by a metal and a non-metal element; at this time, the surface layer 1 and the bottom layer 2 are respectively denoted as support layer 1 and support layer 2.

[0018] In a preferred embodiment of the present invention, the thermoplastic material is a polyester film, a resin film, a polyolefin film, a TPU substrate or a hot melt adhesive film; the hot melt adhesive film includes but is not limited to a silicone soft film, a GORE-TEX film, a PVC film, a PA hot melt adhesive film. Other mesh membranes with heat composite, pressure composite, hot pressing composite and normal temperature and pressure bonding functions are applicable to the present invention.

[0019] In a preferred embodiment of the present invention, the particle sizes of the metal and the compounds formed by the metal and non-metal elements are all 1 nm to 100 μm.

[0020] The second technical solution of the present invention is a heavy-atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection prepared by the above preparation method.

[0021] The present invention discloses the following technical effects:

[0022] The present invention provides a large-scale mass production process for the above heavy-atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection, realizing the large-scale mass production of large-area heavy-atom metal thin film materials, reducing the forming energy consumption and cost of the metal thin film materials, and improving the production efficiency of such thin films.

[0023] The heavy-atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection provided by the present invention solves the problem of difficult film formation of such heavy-atom metals by compounding the powder of the heavy-atom metal material or its short fiber structure with an organic thin film or mesh for lamination to form a metal thin film with nuclear radiation and nuclear, biological and chemical integrated protection capabilities.

[0024] The present invention designs a specific composite structure to effectively shield high-energy X and γ-ray radiations with photon energies in the range of 30 keV - 1.3 MeV, especially high-energy X and γ-ray radiations with photon energies near 130 keV. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention, and those of ordinary skill in the art can also obtain other drawings based on these drawings without creative efforts.

[0026] Figure 1 Schematic diagrams of the structures of the heavy-atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection in the present invention before and after compounding Figure 1 ;

[0027] Figure 2 Schematic diagrams of the structures of the heavy-atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection in the present invention before and after compounding Figure 2 ;

[0028] Figure 3 Surface morphology diagram of the mesh with heavy-atom metal powder hung in the three-dimensional layer in Example 2;

[0029] Figure 4 Schematic diagram of the heavy atom metal powder film forming equipment in the present invention;

[0030] Figure 5 Absorption spectrum of X-rays by the flexible metal thin film material containing tungsten powder in Example 1;

[0031] Figure 6 Absorption spectrum of X-rays by the flexible metal thin film material containing bismuth powder in Example 2. Detailed implementation manners

[0032] The various exemplary implementation manners of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation manners of the present invention.

[0033] It should be understood that the terms used in the present invention are only for describing specific implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0034] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0035] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific implementation manners of the present invention specification, which are obvious to those skilled in the art. Other implementation manners obtained from the present invention specification are obvious to those skilled in the art. The present invention specification and examples are only exemplary.

[0036] Regarding the terms "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.

[0037] The structure of the heavy atom flexible metal thin film material provided by the present invention for nuclear radiation and nuclear, biological, and chemical integrated protection before lamination, as shown in Figure 1The structure shown in the left part, which includes an organic film and a functional layer. The organic film includes, but is not limited to, polyester films, polyolefin films, TPU substrates, and other types of hot-melt adhesive films, silicone soft films, GORE-TEX films, PVC films, PA hot-melt adhesive films, release films, coated papers, as well as various hot-melt adhesive films, adhesive non-woven fabrics, adhesive nylon fabrics, adhesive polyester fabrics, etc.

[0038] The functional layer therein is formed on the underlying organic film (organic film 2) through a powder-sprinkling device similar to that Figure 4 shown. The functional layers used include, but are not limited to, lead powder, tungsten powder, bismuth powder, tantalum powder, tin powder, rare earth elements and their oxide powders, as well as compounds formed by such heavy atomic elements and carbon, nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium elements. In addition, they also include binary or ternary alloys formed by these elements with each other. The morphology of the metal powder can be regular spherical or short fiber rods, or irregular particles. The effective particle size range of the metal particles is from 0.1 nm to 0.5 mm.

[0039] Figure 2 The support layer 1 shown in and the mesh used for binding with the metal powder are laid flat on the Figure 4 shown conveyor belt. The metal powder to be used is pre-loaded quantitatively in the Figure 4 shown powder-sprinkling machine. The powder-sprinkling machine needs to control the powder discharge amount on the one hand and the uniformity of powder sprinkling on the other hand. So that Figure 1 the metal powder film contained in the composite material shown is formed evenly on the organic film 2, and so that the metal powder is evenly attached to the Figure 2 shown mesh in the three-dimensional layer. Regarding the Figure 2 binding method of the metal powder and the mesh shown, it includes, but is not limited to, the above-mentioned powder-sprinkling binding technology, rubbing the mesh in a container filled with metal powder and other technical means to achieve the binding of the metal powder and the mesh in the three-dimensional layer. Finally, a support layer 2 is covered on the mesh with the attached metal powder and it is sent to the laminating machine at the front end of the conveyor belt for lamination. If necessary, release paper can be used for replication lamination during lamination to prevent the glue from seeping out of the composite material and sticking to the pressing belt in the laminating machine.

[0040] The structure containing upper and lower organic laminating films (organic film 1, organic film 2) and a functional layer, with the assistance of release paper or other inner and outer lining fabric materials, after being pressed by a hot-pressing laminating machine, forms Figure 1The composite material structure shown in the right part of the figure. During the hot pressing process, due to the melting and pressing of the organic film, the metal powder uniformly infiltrates into the interior of the upper and lower organic films to form a film, while maintaining the flexibility of the film. The metal film material formed in this way is significantly superior to the film formed by directly mixing metal powder into rubber solution and then laminating in terms of uniformity and radiation protection performance. Because the metal powder will agglomerate under the action of surface energy in the rubber liquid, thus affecting its dispersion uniformity and radiation protection performance. In addition, due to the hot pressing effect, the upper and lower organic films will infiltrate into each other across the intermediate interface. On the one hand, the upper and lower organic films are bonded to each other, well fixing the metal film and its uniformity therein. On the other hand, it can make the final composite material airtight, so that while having the function of nuclear radiation protection, it also has the function of biological and chemical protection.

[0041] It includes upper and lower support layers (support layer 1, support layer 2) and a structure combining a metal powder film network. With the assistance of release paper or directly after being pressed by a hot pressing laminator, it forms Figure 2 The composite material structure shown in the left part of the figure. During the hot pressing process, due to the melting and pressing of the network film, the metal powder uniformly infiltrates into the interior of the network film to form a film. At the same time, the upper and lower surfaces of the network film are bonded to the upper and lower support layers, while maintaining the flexibility of the film. The metal film material formed in this way is also significantly superior to the film formed by directly mixing metal powder into rubber solution and then laminating in terms of uniformity and radiation protection performance.

[0042] The technical solutions described in the present invention, unless otherwise specified, are all conventional solutions in the art. The reagents or raw materials used, unless otherwise specified, are all purchased from commercial channels or have been made public.

[0043] To better understand the present invention, the content of the present invention will be further clarified below in conjunction with embodiments, but the content of the present invention is not limited to the following embodiments.

[0044] Example 1

[0045] A preparation method of a heavy atom flexible metal film material for integrated protection against nuclear radiation and nuclear biological and chemical agents is as follows:

[0046] Before lamination, the metal powder film layer is passed through Figure 4 the equipment shown, evenly covering it on the surface of organic film 2, and then completely covering organic film 1 on the metal powder film layer located on the surface of organic film 2. Finally, with the assistance of release paper covering the outer surfaces of the upper and lower organic films, the above structure is laminated by a laminator. Among them, both organic film 1 and organic film 2 are thermoplastic polyurethane elastic film materials; the metal powder layer is metal tungsten powder with a particle size distribution between 1 nanometer and 100 micrometers; the dosage of tungsten powder is 300 g / m 2 .

[0047] Figure 5 is the absorption spectrum of the heavy-atom flexible metal thin film material in this embodiment for X-rays with energies ranging from 30 keV to 200 keV. As can be seen from Figure 5 , the intrinsic absorption energy of this type of flexible metal thin film is around 80 keV, corresponding to the characteristic absorption spectral line of tungsten element.

[0048] Table 1 shows the radiation protection performance of the heavy-atom flexible metal thin film material in this embodiment for X- and γ-rays. As can be seen from it, this type of heavy-atom flexible metal thin film has good radiation protection performance for X- and γ-rays. In the radiation energy range of 100 keV and below, the protection ratio of the single-layer flexible metal thin film exceeds 20%. Its nuclear protection ratio at 83 keV is -27.28%, which corresponds to Figure 5 the absorption energy spectrum of X-rays shown in

[0049] Table 1

[0050]

[0051] Note: B-1 is the sample number, indicating the sample prepared in Example 1; the reference radiation is the nomenclature in the national standard; the average energy is the average energy of the radiation source, with the unit of keV; the dose rate (shielding material) is the radiation dose received by the radiation detector per unit time after the radiation source is shielded by the shielding material, with the unit of μGy / h; the average value is the average of 10 tests for each radiation energy, with the unit of μGy / h; the protection ratio is the percentage obtained by comparing the average dose rate value for each energy with the average dose rate value of air corresponding to each energy. The negative sign indicates that the energy is absorbed.

[0052] Example 2

[0053] A preparation method of a heavy-atom flexible metal thin film material for nuclear radiation and nuclear biochemical integrated protection is as follows:

[0054] Before lamination, the TPU mesh layer with metal powder is evenly laid on the surface of the support layer 2, and then the support layer 1 completely covers the mesh layer with metal powder on the surface of the support layer 2. Finally, the above structure is laminated by a laminator to obtain the final heavy-atom flexible metal thin film material. Among them, both the support layer 1 and the support layer 2 are flexible non-woven fabrics; the metal powder is bismuth powder with a particle size distribution between 1 nanometer and 100 micrometers. The metallic bismuth powder is mounted on the TPU mesh through mechanical-assisted physical adsorption; the dosage of the metallic bismuth powder is 300 g / m 2 .

[0055] Figure 6 is the absorption spectrum of the heavy-atom flexible metal thin film material in this embodiment for X-rays with energies ranging from 30 keV to 200 keV. As can be seen from Figure 6It can be seen that the intrinsic absorption energy of this type of flexible metal film is around 90 keV, corresponding to the characteristic absorption spectral line of bismuth element.

[0056] Table 2 shows the radiation protection performance of the heavy-atom flexible metal film material in this embodiment against X and γ rays. It can be seen that this type of heavy-atom flexible metal film also has good radiation protection performance against X and γ rays. Compared with the radiation protection performance of the flexible metal film material containing tungsten powder against X and γ rays, the radiation protection performance of this type of film against X and γ rays with energies above 100 keV is better. In the radiation energy range of 100 keV and below, the single-layer flexible metal film containing tungsten powder has better radiation protection performance against X and γ rays.

[0057] Table 2

[0058]

[0059] Note: A-1 is the sample number, indicating the sample prepared in Example 2; the reference radiation is the nomenclature in the national standard; the average energy is the average energy of the radiation source, with the unit of keV; the dose rate (shielding material) is the radiation dose received by the radiation detector per unit time after the radiation source is shielded by the shielding material, with the unit of μGy / h; the average value is the average of 10 measurements for each energy, with the unit of μGy / h; the protection ratio is the percentage obtained by comparing the average dose rate of each energy with the average dose rate of the air corresponding to each energy. A negative sign indicates that the energy is absorbed.

[0060] In practical applications, for different nuclear protection application scenarios, the energies of X and γ rays to be protected are different. It is necessary to select different heavy-atom metal powder films to prepare this type of heavy-atom flexible metal film material according to specific protection energy requirements.

[0061] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a heavy atom flexible metal thin film material for nuclear radiation and nuclear, biological and chemical integrated protection, characterized in that, The functional layer is evenly coated between the surface layer 1 and the bottom layer 2, and then hot-pressed; The functional layer is a metal or a compound formed by a metal and a non-metal element; or, the functional layer is a mesh membrane uniformly adsorbing a metal or a compound formed by a metal and a non-metal element; The metal is lead powder, tungsten powder, bismuth powder, tantalum powder, tin powder or rare earth element; The non-metal element is oxygen, carbon, nitrogen, phosphorus, arsenic, sulfur, selenium or tellurium.

2. The preparation method according to claim 1, characterized in that, The rare earth element is cerium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

3. The preparation method according to claim 1, wherein When the functional layer is a metal or a compound formed by a metal and a non-metal element, the amount of the metal or the compound formed by the metal and the non-metal element is: 200 - 3500 g / m 2 ; When the functional layer is a reticular film that uniformly adsorbs metals or compounds formed by metals and non-metallic elements, the dosage of the metals or compounds formed by metals and non-metallic elements is: 200 - 3500 g / m 2 .

4. The preparation method according to claim 1, wherein The surface layer 1 and the bottom layer 2 are both thermoplastic materials, non-woven fabrics, polyester fabrics, nylon fabrics, non-woven fabrics with adhesive, nylon fabrics with adhesive or polyester fabrics with adhesive; When the surface layer 1 and the bottom layer 2 are both thermoplastic materials, the functional layer is a metal or a compound formed by a metal and a non-metal element; When the surface layer 1 and the bottom layer 2 are both non-woven fabrics, polyester fabrics, nylon fabrics, non-woven fabrics with adhesive, nylon fabrics with adhesive or polyester fabrics with adhesive, the functional layer is a mesh membrane uniformly adsorbing a metal or a compound formed by a metal and a non-metal element.

5. The preparation method according to claim 4, wherein, The thermoplastic material is a polyester film, a resin film, a polyolefin film, a TPU substrate or a hot-melt adhesive film.

6. The preparation method according to claim 1, characterized in that, The particle sizes of the metal and the compound formed by a metal and a non-metal element are both 1 nm to 100 μm.

7. A heavy atom flexible metal film material for nuclear radiation and nuclear, biological and chemical integrated protection prepared by the preparation method according to any one of claims 1 to 6.

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