CN114005564A - Flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material and preparation method and application thereof - Google Patents

Flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material and preparation method and application thereof Download PDF

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CN114005564A
CN114005564A CN202111288954.3A CN202111288954A CN114005564A CN 114005564 A CN114005564 A CN 114005564A CN 202111288954 A CN202111288954 A CN 202111288954A CN 114005564 A CN114005564 A CN 114005564A
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bismuth
film
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flexible polymer
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CN114005564B (en
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陈召来
徐志国
朱伟
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Qingdao Kangyuan Marketing Consulting Co ltd
Shandong University
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Shandong University
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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
    • G21F1/12—Laminated shielding materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material
    • G21F3/02—Clothing

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Abstract

The invention belongs to the technical field of radiation protection, and relates to a lead-free perovskite X-ray protection material, a preparation method and application thereof3Bi2X9Wherein A is Cs, K or methylamine; x is I or Br. A of the invention3Bi2X9The material has better performance than that of a lead-containing perovskite protective material, has higher flexibility, safety and stability, and has a radiation protection effect close to that of the lead-containing protective material.

Description

Flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of radiation protection, and relates to a flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The traditional lead protective clothing is dangerous and inflexible, is not easy to move when in work, and particularly for medical staff working beside an X-ray device for a long time, the protective apron of the traditional lead protective clothing preferably has certain flexibility, and meanwhile, the protective material is nontoxic, stable and easy to prepare. However, the commonly used protective materials contain lead widely, are lack of flexibility and complex in structure, an isolation layer needs to be added to block direct contact between lead and a human body, and the production process is difficult to prepare, so that the production process is easy to cause harm to the environment and workers, and the cost and risk are further increased. It is particularly important to obtain a protective material with good environmental stability, thermal stability and flexibility to replace a lead-containing protective material.
The metal halide material is widely researched in the last decade, especially has a wide application prospect in the photoelectric field, and is acknowledged to have low preparation cost, a simple and rapid manufacturing process and flexible potential. Meanwhile, the metal halide material containing heavy atoms has strong absorption capacity for X-rays, so that the single crystal material has wide application prospect on an X-ray detector at present. However, the strong absorption of X-rays does not mean that it is advantageous in the field of radiation protective materials. The reason is that single crystal materials are expensive, difficult to process and fragile, and amorphous materials with a certain thickness (capable of completely absorbing X-rays) are difficult to uniformly prepare in a large area. For example, iodoplumbum methylamine, whose single crystal lacks flexibility, is fragile, and is difficult to synthesize in a large area, while polycrystal is usually submicron in thickness, cannot completely block X-ray, and the material contains lead, and is highly toxic. Metal halides such as iodostannyl methylamine, bromocupronitrile, and iodomanganebutylamine have weak absorption capacity for X-rays due to small atomic number, and cannot be used for preparing radiation-proof materials. Therefore, it is not easy to find a radiation-proof material capable of replacing metal lead with higher flexibility, stability and safety.
In general, researchers know that subgroup elements with large atomic numbers have rare and expensive characteristics, such as Pt and Au, and therefore, subgroup elements are generally considered to exhibit certain disadvantages in the field of radiation-proof materials. However, the chemical properties of the main group elements with large atomic numbers are unstable, oxides which are difficult to process in a large area are easily formed, and a series of problems such as high brittleness and low flexibility of the material are caused, which is very disadvantageous for realizing a flexible radiation-proof material, and researchers usually do not think that the main group metal elements can embody certain advantages in the field of radiation-proof materials.
Disclosure of Invention
Based on the technical problems faced by the existing lead-containing protective material, the invention provides a flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material, a preparation method and application in order to improve the flexibility, safety and stability of the protective material and improve the radiation protection effect. Unexpectedly, the polymers-A of the invention3Bi2X9The composite material has the performance similar to that of lead-perovskite protective material, and has higher flexibility, safety and stability
Specifically, the invention is realized by the following technical scheme:
in the first aspect of the invention, the flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material is a composite film of polymer inorganic nanoparticles, and the inorganic nanoparticles are A stabilized by a surfactant3Bi2X9Wherein A is Cs, K or methylamine; x is I or Br.
In a second aspect of the present invention, a method for preparing a lead-free X-ray shielding material, comprises:
s1 comparing AX with BiX3Dissolving in DMF solvent to obtain A3Bi2X9Adding long-chain surfactant molecule oleic acid oleylamine and poor solvent acetone into the precursor solution to obtain A with the size of nanometer scale3Bi2X9A material;
s2 reaction of A3Bi2X9Mixing the nano-particle solution and the polymer solution, and stirring at 50-70 ℃;
s3 transferring the solution obtained in the step S2 to a substrate to prepare a polymer composite film of polymer-enclosed inorganic nanoparticles.
In a third aspect of the invention, the radiation-proof fabric comprises a radiation-proof layer, and the radiation-proof layer comprises the lead-free X-ray protection material or the material prepared by any preparation method.
In the fourth aspect of the invention, the garment is made of the radiation-proof fabric.
In a fifth aspect of the invention, a radiation protection device, wherein the material with radiation protection function in the device comprises any of the lead-free X-ray protection materials or the material prepared by any preparation method.
One or more embodiments of the present invention have the following advantageous effects:
(1) the polymer and the surfactant are introduced into the polymer-inorganic nanoparticle composite film, so that the crystal grain size of the inorganic component is regulated to a micro-nano scale, the inorganic component is prevented from being aggregated, the film material is ensured to have flexibility and X-ray blocking property, the stability of the protective material is improved, and the radiation-proof effect is improved.
(2) The preparation method is simple, the cost is low, the prepared material has good environmental stability, the X-ray absorption capacity is strong, the safety is high, and the Cs has flexibility3Bi2I9Polymer film to make X-ray radiation protection device.
(3) By adjusting the thickness of the composite film, the protective effect of different lead equivalent weights can be realized, thereby meeting the requirements of various applications. Compared with lead emphasis, the composite film has 30% reduction of lead emphasis under the same lead equivalent, and simultaneously has excellent flexibility
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows PVDF-Cs after dropping3Bi2I9Compounding the film product;
FIG. 2 shows Cs3Bi2I9And (4) testing thermal stability.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In one or more embodiments of the invention, a flexible polymer-bismuth halide nanoparticle composite X-ray protective material is provided, the protective material is a composite film of polymer inorganic nanoparticles, which ensures that the film material has flexibility and X-ray blocking properties, and the inorganic nanoparticles are A stabilized by a surfactant3Bi2X9Wherein A is Cs, K or methylamine; x is I or Br.
The protective material with the structure has stronger X-ray blocking effect and is beneficial to improving the radiation protection effect. The polymer wraps the inorganic nano particles, so that the stability of the protective material is greatly improved, and the flexibility of the film is favorably ensured. The polymer and the surfactant can be used for regulating and controlling the size of inorganic nanoparticles in the membrane material under the combined action, so that the reduction of flexibility caused by aggregation is avoided.
Further, the polymer is selected from polymethyl methacrylate, polyacrylic acid, polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene or polystyrene; in order to improve the flexibility and stability of the protective material, preferably, the polymer is polyvinylidene fluoride.
Further, the thickness of the polymer composite film is 0.01-2 mm.
The inventor finds that the inorganic nanoparticles are Cs3Bi2I9The prepared polymer composite film has the best flexibility, the best radiation-proof effect and the best stability, and is beneficial to prolonging the service life of the protective material.
In one or more embodiments of the present invention, a method for preparing a flexible polymer-bismuth-based halide nanoparticle composite X-ray shielding material, comprises:
s1 comparing AX with BiX3Dissolving in DMF solvent to obtain A3Bi2X9Adding long-chain surfactant molecule oleic acid oleylamine and poor solvent acetone into the precursor solution to obtain A with the size of nanometer scale3Bi2X9A material;
s2 reaction of A3Bi2X9Mixing the nano-particle solution and the polymer solution, and stirring at 50-70 ℃;
s3 transferring the solution obtained in the step S2 to a substrate to prepare a polymer composite film of polymer-enclosed inorganic nanoparticles.
Further, in S1, AX and BiX3The molar ratio of (A) to (B) is 1-5: 1-3; preferably, it is 3: 2. A. the3Bi2X9The ratio to the surfactant was 10: 1-1: 1; preferably, it is 5: 1. The volume ratio of DMF to poor solvent is 1:5-1: 20; preferably 1: 10. The poor solvent can be acetone, isopropanol, chloroform; among them, acetone is preferred. The long-chain surfactant molecules are oleic acid, oleylamine and dodecyl sulfonate; oleic acid is preferred. The proportion of raw materials is controlled, so that nanoparticles with better size can be obtained, the processing is easier, and the flexible composite film can be formed by the nanoparticles and the polymer.
Wherein is based onAppropriate amount of solvent added, A3Bi2X9The concentration in the solvent DMF was 200-500 mg/ml.
After dissolution in DMF solvent, stirring at 50-70 deg.C, preferably 60 deg.C, helps to maintain clarity and dispersibility of the precursor solution and avoids particle aggregation.
For S2, the concentration of polymer in solvent DMF was 50-200mg/ml based on the appropriate amount of solvent added; preferably, it is 100 mg/mL. Polymers with A3Bi2X9In a ratio of 1:1 to 1: 5; preferably, it is 1: 3. Under the reaction condition, the flexibility can be controlled, and the blocking capability of the composite film on X-rays can be guaranteed. The surfactant molecule is matched with the polymer to act, so that not only can a specific composite structure of the polymer inorganic nano particles be obtained, but also the flexibility of the polymer composite film can be improved, which is not disclosed in the prior art.
In S3, preparing a composite film by one or more of spin coating, blade coating, spray coating and drop coating; or, after obtaining the film, annealing at 70-140 ℃ for 10-30 min; preferably, the annealing temperature is 100 ℃ and the annealing time is 15 min.
The protective material which has no environmental hazard, high flexibility and strong ray absorption capacity is prepared by adopting processes such as spin coating, blade coating, drop coating, spray coating or other mixing methods, not only ensures the high absorption capacity of rays, but also reduces the preparation cost and the process complexity and basically avoids the risk of the preparation process.
In one or more embodiments of the invention, the radiation protection fabric comprises a radiation protection layer, and the radiation protection layer comprises any one of the flexible polymer-bismuth-based halide nanoparticle composite X-ray protection materials or a material prepared by any preparation method. The protective material obtained by the invention has better flexibility, stability and radiation protection effect, so the prepared radiation protection fabric has better advantages.
The structure of the fabric and the like can be designed by those skilled in the art based on the protective material provided by the invention, and fabrics with different structures belong to the protection scope of the invention.
In one or more embodiments of the invention, the garment made of the radiation-proof fabric is made of a protective material with better flexibility, so that the user experience is more comfortable, the radiation-proof effect is better, and the safety of the user is improved.
In one or more embodiments of the invention, a radiation protection device is provided, wherein the material with radiation protection function in the device comprises any one of the flexible polymer-bismuth-based halide nanoparticle composite X-ray protection materials or a material prepared by any preparation method.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9Adding oleic acid into the precursor solution, wherein the concentration of the oleic acid is 50mg/ml, and adding 10 times of volume of isopropanol.
3) To this was added polymethyl methacrylate to give a polymethyl methacrylate concentration of 200 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 200 mu m and the thickness of 25cm2A film. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A200 μm thick film was obtained.
Example 2
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in a molar ratio ofDissolved in DMF solvent and stirred at 60 ℃ to form clear 50mg/ml Cs3Bi2I9Oleic acid was added to the precursor solution at a concentration of 5mg/ml, and isopropanol was added in an amount of 10 times the volume of the precursor solution.
3) To this was added polymethyl methacrylate to give a polymethyl methacrylate concentration of 50 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 10 mu m and the thickness of 25cm2A film of (2). Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A film of 10 μm thickness was obtained.
Example 3
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9Adding oleic acid into the precursor solution, wherein the concentration of the oleic acid is 50mg/ml, and adding 10 times of volume of isopropanol.
3) To this was added polymethyl methacrylate to give a polymethyl methacrylate concentration of 100 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 150 mu m and the thickness of 25cm2A film of (2). Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A150 μm thick film was obtained.
Example 4
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9Adding oleylamine into the precursor solution, wherein the concentration of oleylamine is 50mg/ml, and adding acetone with the volume being 10 times that of the oleylamine.
3) To this was added polymethyl methacrylate to give a polymethyl methacrylate concentration of 100 mg/ml.
4) Dripping 100 mul of solution on the substrate cleaned in the step (1), controlling the thickness of a scraper to be maximum, and carrying out blade coating at a slow speed to obtain the substrate with the thickness of 150 mu m and the thickness of 25cm2A film of (2). Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A film of 70 μm thickness was obtained.
Example 5
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to give clear 200mg/ml Cs3Bi2I9Adding oleylamine into the precursor solution, wherein the concentration of oleylamine is 40mg/ml, and adding acetone with the volume 5 times that of the oleylamine.
3) Polyvinylidene fluoride is added into the mixture to ensure that the concentration of the polyvinylidene fluoride is 100 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 20 mu m and the thickness of 25cm2A film of (2). Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A film of 20 μm thickness was obtained.
Example 6
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to give clear 200mg/ml Cs3Bi2I9Adding oleylamine into the precursor solution, wherein the concentration of oleylamine is 40mg/ml, and adding acetone with the volume 5 times that of the oleylamine.
3) Polyvinylidene fluoride is added into the mixture to ensure that the concentration of the polyvinylidene fluoride is 200 mg/ml.
4) And (3) dropwise adding 100 mu l of solution on the substrate cleaned in the step (1), controlling the thickness of a scraper to be maximum, and carrying out blade coating at a slow speed to obtain a film with the thickness of 30 mu m. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A film of 20 μm thickness was obtained.
Example 7
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to give clear 200mg/ml Cs3Bi2I9Adding sodium dodecyl sulfate into the precursor solution, wherein the concentration of the sodium dodecyl sulfate is 50mg/ml, and adding 10 times of volume of acetone into the precursor solution.
3) Polyvinylidene fluoride is added to ensure that the concentration of the polyvinylidene fluoride is 50 mg/ml.
4) And (3) dropwise adding 100 mu l of solution on the substrate cleaned in the step (1), controlling the thickness of a scraper to be maximum, and carrying out blade coating at a slow speed to obtain a film with the thickness of 5 mu m. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A film of 5 μm thickness was obtained.
Example 8
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 10cm by 10cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9Adding oleic acid oleylamine into the precursor solution, wherein the concentration of the oleic acid oleylamine is 100mg/ml, and adding acetone with the volume being 10 times that of the oleic acid oleylamine.
3) Polyvinylidene fluoride is added into the mixture to ensure that the concentration of the polyvinylidene fluoride is 200 mg/ml.
4) And (2) dripping 500 mu l of solution on the substrate cleaned in the step (1), controlling the thickness of a scraper to be maximum, and carrying out blade coating at a slow speed to obtain a film with the thickness of 100 mu m. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A film of 100 μm thickness was obtained.
Example 9
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 10cm by 10cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9Adding oleylamine into the precursor solution, wherein the concentration of oleylamine is 50mg/ml, and adding acetone with the volume being 10 times that of the oleylamine.
3) Polystyrene was added thereto to ensure a polystyrene concentration of 200 mg/ml.
4) Dripping 5ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 200 mu m and the thickness of 100cm2A film of (2). Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A200 μm thick film was obtained.
Example 10
Flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9Adding oleylamine into the precursor solution, wherein the concentration of oleylamine is 100mg/ml, and adding acetone with the volume 5 times that of the oleylamine.
3) Polystyrene was added thereto to ensure a polystyrene concentration of 200 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 200 mu m and the thickness of 25cm2A film. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A200 μm thick film was obtained.
Example 11:
flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) Mixing KI and BiI3And (3): 2 in DMF solvent and stirring at 60 ℃ to form clear 400mg/ml K3Bi2I9Adding oleic acid oleylamine into the precursor solution,at a concentration of 50mg/ml, 10 volumes of acetone were added.
3) Polystyrene was added thereto to ensure a polystyrene concentration of 200 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 150 mu m and the thickness of 25cm2A film. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A150 μm thick film was obtained.
Example 12:
flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material
1) Cleaning a glass substrate 5cm by 5cm
2) CsBr and BiBr3And (3): 2 in DMF solvent and stirred at 60 ℃ to give clear 350mg/ml Cs3Bi2I9Adding oleylamine into the precursor solution, wherein the concentration of oleylamine is 50mg/ml, and adding acetone with the volume being 10 times that of the oleylamine.
3) Polystyrene was added thereto to ensure a polystyrene concentration of 100 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 100 mu m and the thickness of 25cm2A film. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade to obtain a film with the thickness of 100 mu m.
Comparative example 1:
1) cleaning a glass substrate 5cm by 5cm
2) Mixing CsI and BiI3And (3): 2 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml Cs3Bi2I9And (3) precursor solution.
3) To this was added polymethyl methacrylate to give a polymethyl methacrylate concentration of 200 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 200 mu m and the thickness of 25cm2A film. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A200 μm thick film was obtained.
Comparative example 2:
1) cleaning a glass substrate 5cm by 5cm
2) Mixing CsI with PbI2Mixing the raw materials in a ratio of 1:1 in DMF solvent and stirred at 60 ℃ to form clear 500mg/ml CsPbI3Adding oleic acid into the precursor solution, wherein the concentration of the oleic acid is 50mg/ml, and adding 10 times of volume of isopropanol.
3) To this was added polymethyl methacrylate to give a polymethyl methacrylate concentration of 200 mg/ml.
4) Dripping 1ml of solution on the substrate cleaned in the step (1), and volatilizing the solution to obtain the substrate with the thickness of 200 mu m and the thickness of 25cm2A film. Annealing at 140 deg.C for 15 min.
5) Hanging the film obtained in the step (4) by a blade. A200 μm thick film was obtained.
The materials of example 1, example 11, example 12, comparative example 1 and comparative example 2 were subjected to a performance test:
and (3) flexibility test: folding repeatedly like a sheet
Figure BDA0003333880600000101
And (3) testing the radiation protection performance:
the 200 μm thick film was tested for its blocking properties against X-rays of 50KeV
Figure BDA0003333880600000102
And (3) quality testing: the same lead equivalent, compared to the mass of the lead plate, is lighter than a metal lead plate.
Figure BDA0003333880600000103
Figure BDA0003333880600000111
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material is characterized in that the protective material is a composite film of polymer inorganic nanoparticles, and the inorganic nanoparticles are A stabilized by a surfactant3Bi2X9Wherein A is Cs, K or methylamine; x is I or Br.
2. The flexible polymer-bismuth-based halide nanoparticle composite X-ray shielding material as claimed in claim 1, wherein the polymer is selected from the group consisting of polymethyl methacrylate, polyacrylic acid, polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene and polystyrene.
3. The flexible polymer-bismuth halide nanoparticle composite X-ray shielding material as claimed in claim 1, wherein the thickness of the polymer composite film is 0.01-2 mm.
4. A preparation method of a flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material is characterized by comprising the following steps:
s1 comparing AX with BiX3Dissolving in DMF solvent to obtain A3Bi2X9Adding long-chain surfactant molecule oleic acid oleylamine and poor solvent acetone into the precursor solution to obtain A with the size of nanometer scale3Bi2X9A material;
s2 reaction of A3Bi2X9Nanoparticle solutions and polymerizationMixing the solutions, and stirring at 50-70 deg.C;
s3 transferring the solution obtained in the step S2 to a substrate to prepare a polymer composite film of polymer-enclosed inorganic nanoparticles.
5. The method of claim 4, wherein in S1, AX and BiX are used as the material3The molar ratio of (A) to (B) is 1-5: 1-3; preferably, 3: 2; a. the3Bi2X9The ratio to the surfactant was 10: 1-1: 1; preferably, it is 5: 1. The volume ratio of DMF to poor solvent is 1:5-1: 20; preferably 1: 10. The poor solvent can be acetone, isopropanol, chloroform; among them, acetone is preferred.
Or, after dissolving in DMF solvent, stirring at 50-70 deg.C, preferably 60 deg.C;
alternatively, the concentration of the polymer in the solvent DMF is 50-200 mg/ml.
6. The method for preparing the flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material as claimed in claim 4, wherein in S2, the polymer is mixed with A3Bi2X9In a ratio of 1:1 to 1: 5; preferably, 1: 3;
or, the long chain surfactant molecule is selected from oleic acid, oleylamine, sodium dodecyl sulfate; preferably, oleic acid.
7. The method of claim 4, wherein in S3, the composite film is prepared by one or more of spin coating, blade coating, spray coating, and drop coating; or, after obtaining the film, annealing at 70-140 ℃ for 10-30 min; preferably, the annealing temperature is 100 ℃ and the annealing time is 15 min.
8. A radiation-proof fabric, which is characterized by comprising a radiation-proof layer, wherein the radiation-proof layer comprises the flexible polymer-bismuth-based halide nanoparticle composite X-ray protective material as claimed in any one of claims 1 to 3 or the material prepared by the preparation method as claimed in any one of claims 4 to 7.
9. A garment made of the radiation protective fabric of claim 8.
10. A radiation protection device, characterized in that the device has a radiation protection function, and the device comprises a flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material as claimed in any one of claims 1 to 3 or a material prepared by the preparation method as claimed in any one of claims 4 to 7.
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