CN115467091A - Composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and preparation method thereof - Google Patents
Composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and preparation method thereof Download PDFInfo
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
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Abstract
The invention relates to a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and a preparation method thereof, wherein the composite material is formed by alternately stacking the bismuth oxide/gadolinium oxide nanofiber membranes, and the preparation method comprises the following steps: introducing a polymer into inorganic sol containing bismuth and gadolinium to obtain a precursor solution; preparing a bismuth oxide/polymer hybrid nanofiber membrane and a gadolinium oxide/polymer hybrid nanofiber membrane by using an electrostatic spinning method; removing the polymer to prepare a bismuth oxide nanofiber membrane and a gadolinium oxide nanofiber membrane; and alternately stacking the bismuth oxide nanofiber membrane and the gadolinium oxide nanofiber membrane to obtain the composite material. Compared with the prior art, the composite material provided by the invention has the shielding efficiency of more than 90% on X-rays below 150keV, and solves the problems of large brittleness and difficult forming of the conventional electrostatic spinning bismuth oxide and gadolinium oxide nano-fibers.
Description
Technical Field
The invention relates to the technical field of novel composite materials, in particular to a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and a preparation method thereof.
Background
The X-ray is used as a short-wave ionizing radiation source and is widely applied in the fields of national defense construction, industrial flaw detection, medical treatment and health and the like. However, the overdose of X-ray radiation may cause harm to human body, damage to human organs and tissues, and cause radiation diseases and even death. The X-ray protective clothing can effectively reduce the damage of X-ray radiation to human bodies, and the traditional preparation materials are generally lead-containing materials which are harmful to human bodies, difficult to recover and pollute the environment. In recent years, there has been an increasing research on lead-less or lead-free X-ray radiation-shielding materials.
In recent years, researchers have conducted a series of studies on lead-free wearable radiation protective clothing. Polypropylene is used as a matrix, powder containing lead and barium is used as a shielding agent, and the mixture is granulated and melt-spun to prepare an X-ray-proof composite fiber and non-woven fabric, so that the X-ray-proof protective clothing is prepared; modified polyethylene and polyvinyl chloride are used as shielding fabrics in the United states, and metal tantalum is used as a shielding interlayer between the two fabrics, so that radiation-proof fabrics and whole body radiation-proof clothes are developed. Patent CN101137285A discloses a composite shielding material for medical X-ray protection, which is prepared by adding barium, cadmium, tin and lanthanide into high molecular materials such as natural rubber, etc. to overcome the defect of weak absorption region caused by using single element, but the addition of multiple elements makes the preparation process of the material complicated, and the elements are expensive, which is not beneficial to industrial production.
Bismuth and gadolinium elements have complementary K absorption edges, can realize full-wave-band absorption of X-rays below 150keV, are green and environment-friendly and easily available in raw materials, and have become the key and leading edge of research in the field of nuclear protection. But it is typically added to the polymer matrix in powder form to provide good mechanical properties to the protective garment to meet wearable requirements. However, the high molecular material itself has low interfacial compatibility, and the material itself has a void problem, which results in poor dispersibility, low mechanical properties, and a shielding leak. Therefore, there is a need to develop a pure bismuth oxide/gadolinium oxide composite material that is lightweight, breathable, and capable of efficiently shielding all-band X-rays.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and a preparation method thereof, so that the defects of poor dispersibility, low mechanical property and shielding holes when bismuth and gadolinium are added into a polymer matrix in a powder form are overcome, and the shielding efficiency of the prepared composite material on X-rays below 150keV can reach over 90 percent.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber films, which comprises the following steps:
s1, dissolving a polymer A in N, N-dimethylformamide, and stirring at room temperature for 2-12 h until a homogeneous system is formed to obtain a polymer solution B;
s2, adding a bismuth source into the polymer solution B obtained in the S1, and stirring for 2-6 h at room temperature to obtain a clear and transparent precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector to perform air jet assisted electrostatic spinning, adding an air flow traction area into a classic jet flow flight area, greatly improving the jet speed of the precursor spinning solution C at a jet hole under the synergistic effect of a high-voltage electric field and high-speed air flow, stretching the precursor spinning solution C to form jet flow, and depositing the jet flow on a receiving device to obtain the bismuth oxide/polymer hybrid micro-nano fiber membrane with uniform appearance and without adhesion;
s4, calcining the bismuth oxide/polymer hybrid micro-nano fiber membrane obtained in the S3 as a template to obtain a bismuth oxide nano fiber membrane;
s5, dissolving the polymer D in absolute ethyl alcohol, and uniformly stirring by magnetic force to obtain a polymer solution E;
s6, dissolving a gadolinium source in water, mixing with the polymer solution E obtained in S5, and performing water bath ultrasonic magnetic stirring for 20-48 h to obtain a precursor solution F containing gadolinium;
s7, taking the aluminum foil as a receiving base material, and carrying out electrostatic spinning on the precursor solution D obtained in the S6 under the voltage of 15-100 kV to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the step S7 in an environment with the temperature higher than the decomposition temperature of the polymer and lower than the crystalline phase transition temperature of gadolinium oxide overnight, and removing the polymer in the fiber membrane to obtain a gadolinium oxide nanofiber membrane;
and S9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes.
Preferably, the polymer in S1 is any one of polyethylene oxide (PEO, molecular weight of 100000 to 1000000), polyvinyl alcohol (PVA, molecular weight of 16000 to 200000), polyvinyl butyral (PVB, molecular weight of 30000 to 40000), polyvinyl pyrrolidone (PVP, molecular weight of 45000 to 58000), polyacrylonitrile (PAN, molecular weight of 50000 to 150000).
Preferably, the bismuth source in S2 is any one of bismuth nitrate, bismuth isopropoxide, bismuth acetate, bismuth chloride octahydrate, bismuth subcarbonate, and bismuth oxychloride.
Preferably, the mass ratio of the bismuth source to the polymer solution B in S2 is 1: (1.5-5).
Preferably, the environment of the electrostatic spinning in S3 is: the air humidity is 60-85%, and the temperature is 15-25 ℃.
Preferably, the process parameters of the electrostatic spinning in S3 are: the voltage is 20-120 kV, the perfusion speed is 0.5-15 mL/h, the spinning distance is 15-60 cm, the sliding table speed is 1-200 cm/min, the roller speed of a receiving device is 10-50 r/min, and the air flow speed is 1-20 m/s.
Preferably, the heating rate of the calcination in S4 is 5 ℃/min to 20 ℃/min, the maximum calcination temperature is 400 ℃ to 670 ℃, and the calcination time is 10 to 20 hours.
Preferably, the polymer D in S5 is any one of polyethylene oxide (PEO, molecular weight of 100000 to 1000000), polyvinyl alcohol (PVA, molecular weight of 16000 to 200000), polyvinyl butyral (PVB, molecular weight of 30000 to 40000), polyvinyl pyrrolidone (PVP, molecular weight of 45000 to 58000), and polyacrylonitrile (PAN, molecular weight of 50000 to 150000).
Preferably, the mass fraction of the polymer D in the precursor solution F in S6 is 2-10%, and the mass fraction of the gadolinium source is 4-15%.
Preferably, the gadolinium source in S6 is any one of gadolinium nitrate, gadolinium acetate, gadolinium isopropoxide and gadolinium chlorohydrate.
Preferably, the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber films in S9 is reinforced by a full-contact laminating hot rolling technology of adhesive dispensing.
Further preferably, the process parameters of the point-gluing full-contact lamination hot rolling technology are as follows: the dispensing array is in a multi-array form, the hot rolling temperature is 80-120 ℃, and the dispensing number is 30-100/m 2 The dispensing shape is any one of an ellipse, a triangle, a square or a hexagon.
The second purpose of the invention is to provide a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber films, which is prepared based on the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with the existing elastic lead-free nuclear protective clothing, the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes provided by the invention has the advantage that the shielding efficiency of the material on X-rays below 150keV can reach more than 90% by alternately stacking the inorganic bismuth oxide nanofiber membranes and the gadolinium oxide nanofiber membranes with complementary K-layer absorption edges.
2) The preparation method of the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes provided by the invention is a continuous process, and by combining a sol-gel method and an electrostatic spinning method, and adding an airflow drafting zone in an electrostatic jet flight zone, the flexible bismuth oxide nanofiber membranes and gadolinium oxide nanofiber membranes are successfully prepared, so that the problems of high brittleness and difficulty in forming of the conventional electrostatic spinning bismuth oxide and gadolinium oxide nanofibers are solved, and the method can be applied in a large scale and has better universality.
Drawings
Fig. 1 is a schematic structural diagram of the alternative stacking of the bismuth oxide/gadolinium oxide nanofiber membranes in the technical solution.
Fig. 2 is an electron microscope image and a flexibility display image of the bismuth oxide nanofiber film in example 1.
FIG. 3 is an electron microscope image and a flexibility display image of the gadolinium oxide nanofiber membrane in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the technical scheme, characteristics such as preparation means, materials, structures or composition ratios and the like which are not explicitly described are all regarded as common technical characteristics disclosed in the prior art.
The technical scheme fully realizes the defects of complicated material preparation process, high element price and inconvenience for industrial production of the existing elastic lead-free nuclear protective clothing in the prior art in the conception process; bismuth and gadolinium are added into a polymer matrix in a powder form, and the defects of poor dispersibility, low mechanical property and shielding holes of the material are caused by low interfacial compatibility of a high polymer material, the problem of gaps of the material and the like. Introducing a polymer template into bismuth-containing and gadolinium-containing inorganic sol to obtain a polymer/inorganic sol precursor solution, and preparing flexible bismuth oxide nano-fibers and gadolinium oxide nano-fibers by using an electrostatic spinning method. In the process, the airflow drafting area is added in the jet flow flying process, so that the spinning jet flow is drafted and refined, and finally randomly deposited on the receiving device. And then, the hybrid nanofiber membrane is subjected to gradient heating calcination to remove organic polymer components in the fiber membrane, so that the preparation of flexible pure bismuth oxide fibers and gadolinium oxide nanofibers is realized. In the gradient temperature rise process, the bismuth source and the gadolinium source are respectively and uniformly distributed inside and on the surface of the hybrid nanofiber, when the gradient temperature rise process is regulated and controlled, the form of crystal grains generated by the bismuth source and the gadolinium source can be accurately regulated and controlled, the bismuth oxide nanofiber and the gadolinium oxide nanofiber are formed by small bismuth oxide crystal grains and gadolinium oxide crystal grains, the small crystal grains are continuously fused and grown in the sintering process, the crystal growth process is completed, the original nanofiber is gradually thickened due to the growth of the small crystal grains, and the separation trend is generated, so that the chain-shaped flexible bismuth oxide nanofiber film and the chain-shaped flexible gadolinium oxide nanofiber film are formed. And then alternately stacking the bismuth oxide/gadolinium oxide nanofiber films to obtain the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber films.
Fig. 1 is a schematic structural diagram of a composite material in which bismuth oxide/gadolinium oxide nanofiber films are alternately stacked in the present embodiment.
Example 1
The preparation method of the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in the embodiment comprises the following steps:
s1, adding 0.5g of polyacrylonitrile (PAN, molecular weight 90000) into 9.5g of N, N-Dimethylformamide (DMF), and stirring at room temperature for 4h to prepare a homogeneous polymer solution B accounting for 5% by weight;
s2, then adding 2g of bismuth nitrate (Bi (NO) 3 ) 3 ) Adding the solution into 10g of a polymer solution B obtained by 5-percent wt of S1, and stirring the solution at room temperature for 4 hours to obtain a precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector, and performing electrostatic spinning under the process parameter conditions of 30kV of voltage, 0.5mL/h of perfusion speed, 15cm of spinning distance, 10r/min of receiving device roller speed, 10cm/min of sliding table speed and 10m/S of air flow speed in an environment with the air humidity of 70 +/-5% and the temperature of 20 +/-2 ℃ to obtain the bismuth oxide/polymer hybrid micro-nano fiber membrane with the diameter of 100-1000 nm, wherein the bismuth source is uniformly distributed inside and on the surface of the hybrid nano fiber;
s4, putting the bismuth oxide/polymer hybrid micro-nanofiber membrane obtained in the step S3 into a muffle furnace, heating at the speed of 10 ℃/min, and keeping at 450 ℃ for 14h to obtain a bismuth oxide nanofiber membrane with the fiber diameter of 200-400 nm, wherein an electron microscope image and a flexible display image of the bismuth oxide/polymer hybrid micro-nanofiber membrane are shown in FIG 2;
s5, weighing 28g of absolute ethyl alcohol and 2g of polyacrylonitrile (PAN, the molecular weight of 90000), and uniformly stirring by using magnetic force to obtain a polymer solution E;
s6, weighing 5g of gadolinium nitrate (Gd (NO) 3 ) 3 ·6H 2 O), adding 14g of water to completely dissolve the gadolinium oxide precursor solution, mixing the gadolinium oxide precursor solution with the polymer solution E obtained from the stirred S5, and magnetically stirring for 20 hours to obtain a gadolinium oxide precursor solution;
s7, performing electrostatic spinning (air humidity is 50% and temperature is 25 ℃) on the precursor solution under the voltage of 35kV to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the step S7 in a muffle furnace environment at 550 ℃ overnight to remove the polymer in the fiber membrane, so as to obtain a gadolinium oxide nanofiber membrane with the thickness of 50 micrometers and the fiber diameter of 200-800 nm, wherein an electron microscope image and a flexible display image of the gadolinium oxide/polymer hybrid nanofiber membrane are shown in FIG 3;
s9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 for 10 times to obtain a composite material with the bismuth oxide/gadolinium oxide nanofiber membranes alternately stacked, wherein the glue dispensing array is in a multi-array form, the hot rolling temperature is 80 ℃, and the glue dispensing number is 30/m 2 The dispensing shape is oval.
The thickness of the composite material formed by alternately stacking the bismuth oxide/gadolinium oxide nanofiber films prepared by the preparation method is about 2 mm.
Example 2
The preparation method of the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in the embodiment comprises the following steps:
s1, adding 1g of polyethylene oxide (PEO) into 9g of DMF, and stirring for 2 hours at room temperature to prepare a homogeneous polymer solution B accounting for 10 wt%;
s2, adding 1g of bismuth nitrate (Bi (NO) 3 ) 3 ) Adding the bismuth-containing precursor into 3g of the polymer solution B obtained by the step (1) according to the weight percentage, and stirring the mixture for 5 hours at room temperature to obtain a precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C obtained in the step S2 into an injector, and performing electrostatic spinning under the process parameter conditions of the air humidity of 60 +/-5% and the temperature of 20 +/-2 ℃, the voltage of 32kV, the filling speed of 1mL/h, the spinning distance of 20cm, the receiving device roller speed of 12r/min, the sliding table speed of 15cm/min and the air flow speed of 15m/S to obtain a bismuth oxide/polymer hybrid micro-nano fiber membrane with the diameter of 100-1000 nm, wherein a bismuth source is uniformly distributed inside and on the surface of the hybrid nano fiber;
s4, putting the bismuth oxide/polymer hybrid micro-nano fiber membrane obtained in the S3 into a muffle furnace, heating at the speed of 20 ℃/min, and keeping at 550 ℃ for 12 hours to obtain a bismuth oxide nano fiber membrane with the fiber diameter of 200-400 nm;
s5, weighing 28 parts of absolute ethyl alcohol and 3g of Polyacrylonitrile (PAN), and uniformly stirring by magnetic force to obtain a polymer solution E;
s6, weighing 4g of gadolinium nitrate (Gd (NO) 3 ) 3 ·6H 2 O), adding 12g of water to completely dissolve the gadolinium oxide precursor solution, mixing the gadolinium oxide precursor solution with the polymer solution E obtained from the stirred S5, and magnetically stirring for 20 hours to obtain a gadolinium oxide precursor solution;
s7, performing electrostatic spinning (air humidity is 55% and temperature is 27 ℃) on the precursor solution under the voltage of 30kV to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the step S7 in a muffle furnace environment at 600 ℃ overnight to remove the polymer in the fiber membrane, so as to obtain a gadolinium oxide nanofiber membrane with the thickness of 100 micrometers and the fiber diameter of 200-800 nm;
s9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 for 10 times to obtain a composite material with the bismuth oxide/gadolinium oxide nanofiber membranes alternately stacked, wherein the glue dispensing array is in a multi-array form, the hot rolling temperature is 100 ℃, and the glue dispensing number is 50/m 2 The dispensing shape is triangular.
The thickness of the composite material in which the bismuth oxide/gadolinium oxide nanofiber membranes are alternately stacked in the embodiment prepared by the preparation method is about 4 mm.
Example 3
The preparation method of the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes in the embodiment comprises the following steps:
s1, adding 2.5g of polyvinyl butyral (PVB) into 10g of DMF, and stirring for 2 hours at room temperature to prepare a homogeneous polymer solution B accounting for 20 wt%;
s2, then 1g of bismuth nitrate (Bi (NO) 3 ) 3 ) Adding the solution into 1.5g of the polymer solution B obtained by the step (1) of 20 percent by weight, and stirring the solution at room temperature for 6 hours to obtain a precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C solution obtained in the step S2 into an injector, and performing electrostatic spinning under the process parameter conditions of the air humidity of 80 +/-5% and the temperature of 30 +/-2 ℃, the voltage of 35kV, the perfusion speed of 1.5mL/h, the spinning distance of 25cm, the receiving device roller speed of 15r/min, the sliding table speed of 20cm/min and the air flow speed of 20m/S to obtain a bismuth oxide/polymer hybrid micro-nano fiber film with the diameter of 100-1000 nm, wherein a bismuth source is uniformly distributed in the interior and on the surface of the hybrid nano fiber;
s4, putting the bismuth oxide/polymer hybrid micro-nano fiber membrane obtained in the S3 into a muffle furnace, heating at the speed of 5 ℃/min, and keeping at 600 ℃ for 10 hours to obtain a bismuth oxide nano fiber membrane with the fiber diameter of 200-400 nm;
s5, weighing 28g of absolute ethyl alcohol and 4g of Polyacrylonitrile (PAN), and uniformly stirring by magnetic force to obtain a polymer solution E;
s6, weighing 3g of nitreGadolinium (Gd (NO) 3 ) 3 ·6H 2 O), adding 9g of water to completely dissolve the gadolinium oxide precursor solution, mixing the gadolinium oxide precursor solution with the stirred polymer solution E obtained from the S5, and magnetically stirring the mixture for 48 hours to obtain a gadolinium oxide precursor solution;
s7, performing electrostatic spinning (air humidity is 45% and temperature is 20 ℃) on the precursor solution under the voltage of 35kV to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the step S7 in a muffle furnace environment at 580 ℃ overnight to remove the polymer in the fiber membrane, so as to obtain a gadolinium oxide nanofiber membrane with the thickness of 200 microns and the fiber diameter of 200-800 nm;
s9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 for 10 times to obtain a composite material with the bismuth oxide/gadolinium oxide nanofiber membranes alternately stacked, wherein the glue dispensing array is in a multi-array form, the hot rolling temperature is 120 ℃, and the glue dispensing number is 80/m 2 The dispensing shape is hexagonal.
The thickness of the composite material in which the bismuth oxide/gadolinium oxide nanofiber membranes are alternately stacked in the embodiment prepared by the preparation method is about 8 mm.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes is characterized by comprising the following steps:
s1, dissolving a polymer A in N, N-dimethylformamide, and stirring at room temperature for 2-12 hours until a homogeneous system is formed to obtain a polymer solution B;
s2, adding a bismuth source into the polymer solution B obtained in the S1, and stirring for 2-6 h at room temperature to obtain a clear and transparent precursor spinning solution C containing bismuth;
s3, injecting the precursor spinning solution C obtained in the S2 into an injector to perform air jet assisted electrostatic spinning, adding an air flow traction area into a classical jet flow flight area, greatly improving the injection rate of the precursor spinning solution C at a jet hole under the synergistic action of a high-voltage electric field and high-speed air flow, stretching the precursor spinning solution C to form jet flow, and depositing the jet flow on a receiving device to obtain the bismuth oxide/polymer hybrid micro-nano fiber membrane with uniform appearance and no adhesion;
s4, calcining the bismuth oxide/polymer hybrid micro-nano fiber membrane obtained in the S3 as a template to obtain a bismuth oxide nano fiber membrane;
s5, dissolving the polymer D in absolute ethyl alcohol, and uniformly stirring by magnetic force to obtain a polymer solution E;
s6, dissolving a gadolinium source in water, mixing with the polymer solution E obtained in S5, and performing water bath ultrasonic magnetic stirring for 20-48 h to obtain a precursor solution F containing gadolinium;
s7, taking an aluminum foil as a receiving base material, and performing electrostatic spinning on the precursor solution D obtained in the S6 at the voltage of 15-100 kV, the air humidity of 50-85% and the temperature of 20-30 ℃ to obtain a gadolinium oxide/polymer hybrid nanofiber membrane;
s8, placing the gadolinium oxide/polymer hybrid nanofiber membrane obtained in the step S7 in an environment with the temperature higher than the decomposition temperature of the polymer D and lower than the crystalline phase transition temperature of the gadolinium oxide overnight, and removing the polymer D in the gadolinium oxide/polymer hybrid nanofiber membrane to obtain a gadolinium oxide nanofiber membrane;
and S9, alternately stacking the bismuth oxide nanofiber membrane obtained in the S4 and the gadolinium oxide nanofiber membrane obtained in the S8 to obtain the composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes.
2. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes as claimed in claim 1, wherein the polymer a in S1 is any one of polyethylene oxide, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone and polyacrylonitrile.
3. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber films as claimed in claim 1, wherein the bismuth source in S2 is any one of bismuth nitrate, bismuth isopropoxide, bismuth acetate, bismuth chloride octahydrate, bismuth subcarbonate and bismuth oxychloride; the mass ratio of the bismuth source to the polymer solution B in S2 is 1: (1.5-5).
4. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes as claimed in claim 1, wherein the electrospinning environment in S3 is as follows: the air humidity is 55-85%, and the temperature is 15-35 ℃; the electrostatic spinning process parameters in the S3 are as follows: the voltage is 20-120 kV, the perfusion speed is 0.5-15 mL/h, the spinning distance is 15-60 cm, the sliding table speed is 1-200 cm/min, the receiving device roller speed is 10-50 r/min, and the air flow speed is 1-20 m/s.
5. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes as claimed in claim 1, wherein the temperature rise rate of the calcination in S4 is 5 ℃/min to 20 ℃/min, the maximum calcination temperature is 400 ℃ to 670 ℃, and the calcination time is 10 to 20 hours.
6. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes as claimed in claim 1, wherein the polymer D in S5 is any one of polyethylene oxide, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone and polyacrylonitrile.
7. The preparation method of the composite material formed by alternately stacking the bismuth oxide/gadolinium oxide nanofiber membranes according to claim 1, wherein the mass fraction of the polymer D in the precursor solution F in S6 is 2-10%, and the mass fraction of the gadolinium source is 4-15%; the gadolinium source in S6 is any one of gadolinium nitrate, gadolinium acetate, gadolinium isopropoxide and gadolinium chlorohydrate.
8. The method for preparing the composite material formed by alternately stacking the bismuth oxide/gadolinium oxide nanofiber films according to claim 1, wherein the composite material formed by alternately stacking the bismuth oxide/gadolinium oxide nanofiber films in the step S9 is reinforced by a full-contact laminating hot rolling technique of adhesive dispensing.
9. The method for preparing the composite material with the alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes as claimed in claim 8, wherein the process parameters of the full contact type hot rolling technique for adhesive dispensing are as follows: the dispensing array is in a multi-array form, the hot rolling temperature is 80-120 ℃, and the dispensing number is 30-100/m 2 The dispensing shape is any one of an ellipse, a triangle, a square or a hexagon.
10. The composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber films prepared based on the preparation method of any one of claims 1 to 9.
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