CN115467162A - Wave-absorbing composite electromagnetic shielding fiber film and preparation method thereof - Google Patents
Wave-absorbing composite electromagnetic shielding fiber film and preparation method thereof Download PDFInfo
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
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- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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Abstract
The invention belongs to the technical field of electromagnetic shielding, and particularly relates to a wave-absorbing composite electromagnetic shielding fiber film and a preparation method thereof. The invention adopts a polymer fiber film produced by electrostatic spinning as a substrate, and compounds the polymer fiber film with metal nanowires (at least containing one magnetic metal nanowire) to prepare the wave-absorbing type composite electromagnetic shielding fiber film; the metal nanowires can penetrate into the porous structure of the spinning fiber film and be attached to the inside of the porous structure of the spinning fiber film, the metal nanowires have good flexibility, can be effectively combined with fibers, can be always kept conductive and not fall off when being subjected to external stress or deformation, and ensure that the wave-absorbing type composite electromagnetic shielding fiber film has good mechanical property.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding, and particularly relates to a wave-absorbing composite electromagnetic shielding fiber film and a preparation method thereof.
Background
With the rapid development of the era, the 5G era comes, the communication technology is continuously improved, electromagnetic interference is ubiquitous, and the influence on the life of people is greater and greater. The human body belongs to a biological medium, and after electromagnetic radiation reaches a certain intensity, the original balance state of the human body can be destroyed, so that the immune system and the nervous system of the human body are influenced, and the health of people is seriously harmed. Electromagnetic radiation not only affects human health, but also has great influence on the aerospace industry. Under the influence of radio equipment, the professional frequency of civil aviation radio easily receives electromagnetic interference, so that signals cannot be normally received or cannot be received. The arrival of the 5G era means the improvement of the electronic integration level, so that the anti-interference capability of the chip is in a remarkable decline trend, the damage of electromagnetic interference to an integrated circuit can be seen, and the strong electromagnetic interference effect can cause the failure of electronic components.
In general, a material that blocks the propagation of electromagnetic waves by blocking or absorbing energy of the electromagnetic waves so as to reduce the energy is called an electromagnetic shielding material. The electromagnetic shielding effectiveness of such materials is primarily related to electrical conductivity and magnetism. Electromagnetic shielding materials are generally classified into: conductive polymer electromagnetic shielding materials and electromagnetic shielding paints. The conductive polymer electromagnetic shielding material is classified into a composite type and an intrinsic type, and is classified into a metal material, a carbon material and the like according to different filling types. The conductive polymer electromagnetic shielding film in the current market has the problems of poor adhesion of metal powder, easy cracking and peeling and the like, thereby causing poor mechanical property.
Disclosure of Invention
In view of the above, the present invention aims to provide a wave-absorbing composite electromagnetic shielding fiber film and a preparation method thereof, and the wave-absorbing composite electromagnetic shielding fiber film prepared by the preparation method of the present invention has the advantages of strong adhesion of metal nanowires, difficult occurrence of cracking and peeling, and good mechanical properties.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a wave-absorbing composite electromagnetic shielding fiber film, which comprises the following steps:
mixing a polymer and an organic solvent, and performing electrostatic spinning on the obtained electrostatic spinning solution to obtain a polymer electrostatic spinning film;
the mass ratio of the polymer to the organic solvent is (5-20) to (80-95);
the voltage of the electrostatic spinning is 8-30 kV;
mixing a solution of soluble metal salt, a solution of a reducing agent, a nucleating agent and a citrate complexing agent, and carrying out reduction reaction in a magnetic field to obtain a metal nanowire stock solution; the soluble metal salt comprises at least one magnetic soluble metal salt; the concentration of the solution of the reducing agent is 0.05-2 mol/L;
and loading the polymer electrostatic spinning film on the metal nanowires in the metal nanowire stock solution to obtain the wave-absorbing composite electromagnetic shielding fiber film.
Preferably, the electrostatic spinning solution further comprises dielectric nano ceramic powder; the dielectric nano ceramic powder comprises one or more of silicon carbide, silicon nitride, zinc oxide, tin oxide, barium titanate and iron nitride.
Preferably, the magnetic soluble metal salt comprises one or more of soluble nickel salt, soluble cobalt salt and soluble iron salt; the reducing agent comprises hydrazine hydrate.
Preferably, the molar ratio of the soluble metal salt to the reducing agent is 1 (0.5 to 10).
Preferably, the nucleating agent comprises chloroplatinic acid.
Preferably, the citrate complexing agent comprises sodium citrate.
Preferably, the polymer comprises one or more of polyvinylidene fluoride, polyacrylonitrile, hexafluoropropylene and polyetherimide.
Preferably, the organic solvent includes N, N-dimethylformamide and acetone; the volume ratio of the N, N-dimethylformamide to the acetone is 5 (1-9).
Preferably, the loading mode comprises one or more of coating, dipping and suction filtration loading.
The invention also provides the wave-absorbing composite electromagnetic shielding fiber film prepared by the preparation method in the technical scheme, which comprises a polymer electrostatic spinning film and metal nanowires loaded on the surface and in pores of the polymer electrostatic spinning film, wherein the metal nanowires at least comprise one magnetic metal nanowire.
The invention provides a preparation method of a wave-absorbing composite electromagnetic shielding fiber film, which comprises the following steps: mixing a polymer and an organic solvent, and performing electrostatic spinning on the obtained electrostatic spinning solution to obtain a polymer electrostatic spinning film; mixing a solution of soluble metal salt, a reducing agent, a nucleating agent and a citrate complexing agent, and carrying out reduction reaction in a magnetic field to obtain a metal nanowire stock solution; the soluble metal salt comprises at least one magnetic soluble metal salt; and compounding the metal nanowire stock solution and the polymer electrostatic spinning film to obtain the wave-absorbing type composite electromagnetic shielding fiber film.
The invention adopts a polymer fiber film produced by electrostatic spinning as a substrate, and compounds the polymer fiber film with metal nanowires (at least containing one magnetic metal nanowire) to prepare the wave-absorbing type composite electromagnetic shielding fiber film; the polymer fiber film produced by electrostatic spinning is a structure similar to cloth and composed of a plurality of fibers, a plurality of pores are arranged in the film, the film has good air permeability compared with a conventional solid film, the magnetic metal nanowires can penetrate into the porous structure of the spinning fiber film and can be attached to the surface layer of the film material, and the metal nanowires are used as one-dimensional nano materials and have good flexibility.
In addition, the dielectric ceramic powder with good dielectric property is added into the spinning solution, so that the dielectric loss of the wave-absorbing composite electromagnetic shielding fiber film can be reduced.
Drawings
FIG. 1 is an SEM image of magnetic nickel nanowires obtained in example 1;
FIG. 2 is an SEM image of magnetic Ni-Fe nanowires obtained in example 2;
FIG. 3 is an SEM image of the magnetic Ni-Co nanowires obtained in example 3;
FIG. 4 is an SEM image of a polymer electrospun membrane prepared according to example 4;
FIG. 5 is an SEM image of a polymeric electrospun membrane prepared according to example 5;
FIG. 6 is an SEM image of a polymeric electrospun membrane prepared according to example 6;
FIG. 7 is an SEM image of a polymeric electrospun membrane prepared according to example 7;
FIG. 8 is an SEM image of the wave-absorbing composite electromagnetic shielding fiber film prepared in example 4;
fig. 9 is an SEM image of the wave-absorbing composite electromagnetic shielding fiber film prepared in example 5.
Detailed Description
The invention provides a preparation method of a wave-absorbing composite electromagnetic shielding fiber film, which comprises the following steps:
mixing a polymer and an organic solvent, and performing electrostatic spinning on the obtained electrostatic spinning solution to obtain a polymer electrostatic spinning film;
the mass ratio of the polymer to the organic solvent is preferably (5-20) to (80-95);
the voltage of the electrostatic spinning is preferably 8-30 kV;
mixing a solution of soluble metal salt, a solution of a reducing agent, a nucleating agent and a citrate complexing agent, and carrying out reduction reaction in a magnetic field to obtain a metal nanowire stock solution; the soluble metal salt comprises at least one magnetic soluble metal salt; the concentration of the solution of the reducing agent is 0.05-2 mol/L;
and loading the polymer electrostatic spinning film on the metal nanowires in the metal nanowire stock solution to obtain the wave-absorbing composite electromagnetic shielding fiber film.
Unless otherwise specified, the present invention does not require any particular source of the starting materials for the preparation, and commercially available products known to those skilled in the art may be used.
The invention mixes the polymer and the organic solvent to obtain the electrostatic spinning solution.
In the invention, the polymer preferably comprises one or more of polyvinylidene fluoride, polyacrylonitrile, hexafluoropropylene and polyetherimide, and more preferably polyvinylidene fluoride; when the polymers are the above polymers, the proportion of different polymers is not particularly limited, and the polymers can be prepared in any proportion. In the present invention, the organic solvent preferably includes N, N-dimethylformamide and acetone; the volume ratio of the N, N-dimethylformamide to the acetone is 5 (1-9), and more preferably 5 (1-3). In the present invention, the mass ratio of the polymer to the organic solvent is preferably (5 to 20): (80 to 95), more preferably (10 to 20): (80 to 90).
The mass ratio of the polymer to the solvent is limited in the range, so that the problems that too little prepared spinning substrate fiber is not favorable for the adhesion of subsequent metal nanowires due to too low polymer consumption and too much spinning solution is too viscous and is not favorable for application due to too long curing time in the spinning process and too much viscosity is not favorable for the tendency of splitting under the action of electric field force in the spinning process, spinning fibers are thick and more beads exist are avoided.
In the present invention, the polymer and the organic solvent are mixed to dissolve the polymer in the organic solvent. In the present invention, when the organic solvent includes N, N-dimethylformamide and acetone, the dissolution is preferably performed by dissolving the polymer in N, N-dimethylformamide, and mixing with acetone with stirring; the stirring time is preferably 12 to 36 hours, and more preferably 24 to 36 hours. The stirring speed is not particularly limited and can be selected according to actual conditions.
In the present invention, the electrospinning liquid preferably further comprises dielectric nano ceramic powder; the dielectric nano ceramic powder preferably comprises one or more of silicon carbide, silicon nitride, zinc oxide, tin oxide, barium titanate and iron nitride, and more preferably barium titanate; when the dielectric nano ceramic powder is prepared from the above materials, the invention has no special limitation on the proportion of different dielectric nano ceramic powders, and the proportion can be any; the shape structure of the dielectric nano ceramic powder is preferably one or more of a nanowire, a nano chain, a nanoparticle, a nanorod or a nanosheet; when the dielectric nano ceramic powder is prepared from the above materials, the proportion of the dielectric nano ceramic powder with different morphological structures is not specially limited, and the dielectric nano ceramic powder can be prepared at any proportion; the mass ratio of the polymer to the dielectric nano ceramic powder is preferably 100 (1-15), and more preferably 100 (5-10).
The dielectric ceramic powder is added to the invention, so that the obtained film material has a dielectric loss effect, and the dielectric loss in the electromagnetic shielding performance can play a role in attenuating electromagnetic waves, thereby improving the electromagnetic shielding performance of the material.
In the present invention, the dielectric nano ceramic powder is preferably added to a solution obtained by mixing the polymer and the organic solvent, and stirred to obtain the electrospinning solution. The stirring process is not specially limited, and the materials are uniformly mixed.
After the electrostatic spinning solution is obtained, the electrostatic spinning solution is subjected to electrostatic spinning to obtain the polymer electrostatic spinning film.
In the invention, the voltage of the electrostatic spinning is 8-30 kV, preferably 12-20 kV; the push injection speed is preferably 0.01-1 mm/min, and more preferably 0.1-1 mm/min; the distance between the needle and the receiver of the electrospinning is preferably 10 to 15cm, more preferably 10 to 13cm.
The electrostatic spinning voltage is limited within the range, so that the phenomenon that when the spinning voltage is too small, the electrostatic force of the spinning solution is too small along with the increase of the spinning voltage, the voltage of the spinning solution is reduced, the dotted electric jet of the spinning solution has smaller acceleration, the traction force obtained by liquid drops is small, the liquid drops are not beneficial to splitting, and the thickness of the spinning fiber is not uniform while more beads exist in the obtained fiber, so that the adhesion of a subsequent metal nanowire and the mechanical strength of a substrate film are influenced can be avoided; and the electric field force and the traction force can be prevented from increasing when the voltage is overlarge, but the distance between the needle head and the receiving substrate is fixed, when the traction force is overlarge, the acceleration is overlarge, because the receiving distance is relatively too short, the liquid drops are not split and are completely received, the receiving time is too short, the fiber thinning is not facilitated, and large beads are easy to appear.
The present invention mixes a solution of a soluble metal salt, a solution of a reducing agent, a nucleating agent, and a citrate complexing agent.
In the present invention, the soluble metal salt includes at least one kind of magnetic soluble metal salt; the magnetic soluble metal salt preferably comprises one or more of soluble nickel salt, soluble cobalt salt and soluble iron salt, and more preferably soluble nickel salt; when the magnetic soluble metal salts are the above, the proportion of different types of magnetic soluble metal salts is not specially limited, and the proportion can be any; the concentration of the solution of the soluble metal salt is preferably 0.05 to 1mol/L, and more preferably 0.1 to 0.5mol/L; the solution of the soluble metal salt preferably has a pH of 10 to 14, more preferably 12 to 13. The process for adjusting the pH of the solution of soluble metal salt is not particularly limited in the present invention, and may be an adjustment process well known in the art, and in the embodiment of the present invention, the pH of the solution of soluble metal salt is specifically adjusted by alkali liquor.
In the present invention, the soluble metal salt preferably further includes a non-magnetic soluble metal salt; the non-magnetic soluble metal salt is preferably a soluble silver salt; the molar ratio of the magnetically soluble metal salt to the non-magnetically soluble metal salt is preferably 1 (0.1 to 1), more preferably 1 (0.1 to 0.5). The kind of the non-magnetic soluble metal salt is not particularly limited, and may be selected according to actual conditions. The solution of the soluble metal salt at least comprises a magnetic soluble metal salt, so that the metal atoms which are subsequently reduced can be aligned and grown into the nano-wires under the action of an external magnetic field. When the solution of the soluble metal salt comprises magnetic metal ions and non-magnetic metal ions, the magnetic metal is used as a template to guide the growth of the non-magnetic metal in the growth process, and finally the alloy nanowire consisting of the magnetic metal and the non-magnetic metal is prepared.
In the present invention, the reducing agent preferably includes hydrazine hydrate; the concentration of the solution of the reducing agent is preferably 0.05 to 2mol/L, and more preferably 0.5 to 1mol/L; the pH of the reducing agent solution is preferably 10 to 14, more preferably 11 to 13. The process of adjusting the pH of the reducing agent solution is not particularly limited in the present invention, and may be an adjusting process well known in the art, and in the embodiment of the present invention, the pH of the reducing agent solution is specifically adjusted by using an alkali solution.
The concentration of the reducing agent solution is limited within the range, so that the low yield of the metal nanowires caused by the low concentration of the reducing agent solution can be avoided, meanwhile, the low concentration of the reducing agent solution can possibly cause the insufficient reducibility and can not well form a nanowire structure, and the phenomenon that the reducing agent is excessive due to the overhigh reducing agent solution and can cause the reaction rate to be too high, so that the metal nanowires are agglomerated together, and the metal nanowires can not be uniformly dispersed can also be avoided.
In the present invention, the nucleating agent preferably includes chloroplatinic acid; the citrate complexing agent preferably comprises sodium citrate.
In the present invention, the molar ratio of the soluble metal salt to the reducing agent is preferably 1 (0.5 to 10), more preferably 1 (0.5 to 5); the mol ratio of the soluble metal salt to the nucleating agent is preferably 1000 (0.5-10), and more preferably 1000 (0.5-5); the molar ratio of the soluble metal salt to the complexing agent is preferably 1 (0.1 to 1), more preferably 1 (0.1 to 0.5).
In the invention, the process of mixing the solution of the soluble metal salt, the solution of the reducing agent, the nucleating agent and the citrate complexing agent is preferably to add the nucleating agent and the citrate complexing agent into the solution of the soluble metal salt, then preheat the solution of the soluble metal salt and the solution of the reducing agent respectively, and mix the solution of the soluble metal salt and the solution of the reducing agent to obtain a mixed solution of the metal salt and the reducing agent; the preheating is preferably water bath heating; the preheating temperature is preferably 50-100 ℃, and more preferably 60-80 ℃; the preheating time is preferably 5 to 40min, and more preferably 10 to 30min.
After the mixed solution of the metal salt and the reducing agent is obtained, the mixed solution of the metal salt and the reducing agent is subjected to a reduction reaction under a magnetic field to obtain a metal nanowire stock solution.
In the present invention, the intensity of the magnetic field is preferably 0.005 to 1T, more preferably 0.005 to 0.05T; the temperature of the reduction reaction is preferably 50-100 ℃, and more preferably 60-80 ℃; the time of the reduction reaction is preferably 5 to 60min, and more preferably 20 to 45min; the present invention preferably terminates the reduction reaction before agglomeration of the reduction reaction product occurs.
The invention preferably carries out post-treatment on the metal nanowire stock solution. In the invention, the post-treatment preferably comprises dilution, filtration, cleaning and dispersion in sequence to obtain a magnetic metal nanowire dispersion liquid; the solvent used for the dilution is preferably water; the cleaning liquid used for cleaning is preferably water; the filtration mode is preferably vacuum filtration; the dispersion is preferably a dispersion of the washed magnetic metal nanowires in water. The process of dilution, vacuum filtration, washing and dispersion is not particularly limited in the present invention, and the processes of dilution, vacuum filtration, washing and dispersion well known in the art are adopted.
The method adopts a low-temperature water-phase template-free method to prepare the metal nanowires by means of magnetic field induction, a hard template (such as anodized aluminum with vertical holes) or a soft template (such as PVP and other surfactants) is generally needed for preparing nanowire materials, the concentration of system metal ions is reduced along with the reaction, so that metal atoms deposited or grown in the template are reduced, and the size unevenness (including length and diameter) is caused.
The concentration of metal ions in the soluble metal salt solution is limited within the range, on one hand, the metal nanowires obtained are few and low in yield and are not beneficial to application due to too low concentration of the metal ions, and on the other hand, the metal nanowires generated by reduction in a magnetic field due to too high concentration of the metal ions can be avoided, and when the concentration of the nanowires is too high, the nanowires can be agglomerated together and are not beneficial to subsequent compounding with the polymer electrostatic spinning film.
In the present invention, the diameter of the metal nanowire is preferably 30 to 300nm, more preferably 30 to 100nm, and the length is preferably 1 to 100 μm, more preferably 2 to 50 μm; .
The polymer electrostatic spinning film is loaded on the metal nanowires in the metal nanowire stock solution, so that the wave-absorbing composite electromagnetic shielding fiber film is obtained.
In the invention, the loading mode preferably comprises one or more of coating, dipping and suction filtration loading, and more preferably comprises coating or suction filtration loading; the coating preferably comprises one or more of electrostatic spraying, air spraying, airless spraying and blade coating, and more preferably electrostatic spraying, air spraying, airless spraying or blade coating.
In the present invention, the mass ratio of the polymer electrospun membrane to the metal nanowires in the metal nanowire stock solution is preferably 1 (0.001 to 0.5), and more preferably 1 (0.01 to 0.1).
Before compounding, the present invention preferably further comprises cleaning the polymeric electrospun membrane; the cleaning equipment is preferably a plasma cleaning machine; the washing time is preferably 60 to 180 seconds, and more preferably 90 to 120 seconds. The polymer electrostatic spinning membrane is cleaned by the plasma cleaning machine, so that organic matters on the surface of the polymer electrostatic spinning membrane can be removed, the polymer electrostatic spinning membrane can be subjected to hydrophilic modification, the hydrophilicity of the polymer electrostatic spinning membrane is improved, and the subsequent compounding of the metal nanowires and the polymer electrostatic spinning membrane is facilitated.
After the compounding, the compound obtained by compounding is preferably dried to obtain the wave-absorbing type composite electromagnetic shielding fiber film. The drying process is not particularly limited in the present invention, and a drying process well known in the art may be used.
The invention also provides the wave-absorbing composite electromagnetic shielding fiber film prepared by the preparation method in the technical scheme, which is characterized by comprising a polymer electrostatic spinning film and metal nanowires loaded on the surface and in pores of the polymer electrostatic spinning film, wherein the metal nanowires at least comprise one magnetic metal nanowire.
In the present invention, the polymer electrospun membrane is preferably composed of polymer spun fibers, the diameter of the polymer spun fibers is preferably 0.1 to 5 μm, and more preferably 0.1 to 1 μm; the thickness of the polymer electrospun membrane is preferably 50 to 100 μm, and more preferably 70 to 90 μm.
The technical solutions in the present invention will be clearly and completely described below with reference to the embodiments in the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
500mL of metal salt solution (containing NiCl) is prepared 2 0.1mol/L，Na 3 C 6 H 5 O 7 37.5mmol/L，H 2 PtCl 6 0.2×10 -3 mol/L) and adjusting the pH value to 12.5 by using an alkali solution, preparing 500mL of 0.5mol/L hydrazine hydrate solution, adjusting the pH value to 12.5 by using an alkali solution, and mixing a metal salt solution and the hydrazine hydrate solution (the molar ratio of the soluble metal salt to the reducing agent is 1:3.6) Respectively preheating for 30min under the condition of water bath at 60 ℃, mixing, carrying out reduction reaction for 20min under the condition of a magnetic field at 60 ℃ and 0.03T, then adding deionized water into a reduction product for dilution, carrying out vacuum filtration to obtain nickel nanowires, cleaning for three times by using 1L of distilled water, and dispersing the nickel nanowires in water to obtain the magnetic nickel nanowire dispersion liquid.
Example 2
500mL of metal salt solution (containing NiCl) is prepared 2 0.09mol/L，FeCl 3 0.01mol/L，Na 3 C 6 H 5 O 7 37.5mmol/L，H 2 PtCl 6 0.2×10 -3 mol/L), adjusting the pH value to 12.5 with an alkali solution, preparing 500mL of 0.5mol/L hydrazine hydrate solution, adjusting the pH value to 12.5 with the alkali solution, preheating a metal salt solution and the hydrazine hydrate solution (the molar ratio of soluble metal salt to a reducing agent is 1.
Example 3
500mL of metal salt solution (containing NiCl) is prepared 2 0.09mol/L，CoCl 2 0.01mol/L，Na 3 C 6 H 5 O 7 37.5mmol/L，H 2 PtCl 6 0.2×10 -3 mol/L), adjusting the pH value to 12.5 with an alkali solution, preparing 500mL of 0.5mol/L hydrazine hydrate solution, adjusting the pH value to 12.5 with the alkali solution, preheating a metal salt solution and the hydrazine hydrate solution (the molar ratio of a soluble metal salt to a reducing agent is 1.
Example 4
500mL of metal salt solution (which was prepared)In which NiCl is contained 2 0.1mol/L，Na 3 C 6 H 5 O 7 37.5mmol/L，H 2 PtCl 6 0.2×10 -3 mol/L), adjusting the pH value to 13 with an alkali solution, preparing 500mL of 0.5mol/L hydrazine hydrate solution, adjusting the pH value to 13 with the alkali solution, preheating a metal salt solution and the hydrazine hydrate solution (the molar ratio of a soluble metal salt to a reducing agent is 1: 3.6) respectively for 30min under the condition of 60 ℃ water bath, mixing, and carrying out reduction reaction for 30min under the conditions of 60 ℃ and 0.05T magnetic field to obtain a nickel-containing nanowire stock solution;
dissolving polyvinylidene fluoride in N, N-dimethylformamide, adding acetone (the volume ratio of the N, N-dimethylformamide to the acetone is 3:1), stirring for 12-36 h, wherein the mass concentration of the polyvinylidene fluoride is 10%, performing electrostatic spinning under the voltage of 12kV, the pushing injection speed is 0.5mm/min, and the distance between a needle head and a receiver of the electrostatic spinning is 12cm, so as to obtain a polymer electrostatic spinning membrane;
and (3) loading the nickel-containing nanowire stock solution on the polymer electrostatic spinning membrane (cleaned for 120s by using a plasma cleaning agent) by a suction filtration method, compounding, and drying to obtain the wave-absorbing type composite electromagnetic shielding fiber membrane.
Example 5
The difference from example 4 is that the mass concentration of polyvinylidene fluoride is 10%, barium titanate accounting for 50% of the mass of polyvinylidene fluoride is added into polyvinylidene fluoride solution, and the rest is the same as example 4.
Example 6
The difference from example 5 was that the voltage was 14kV, and the rest was the same as example 5.
Example 7
The difference from example 5 was that the voltage was 16kV, and the rest was the same as example 5.
Performance testing
(1) The magnetic nanowires obtained by suction-filtering and drying the nanowire dispersions obtained in examples 1 to 3 were scanned by a scanning electron microscope, and the results are shown in fig. 1 to 3.
As can be seen from FIG. 1, the magnetic nickel nanowires obtained in example 1 had an average diameter of 50nm and an average length of 6 μm.
As can be seen from fig. 2, the magnetic nickel-iron nanowires obtained in example 2 had an average diameter of 49nm and an average length of 4 μm.
As can be seen from FIG. 3, the magnetic Ni-Co nanowires obtained in example 3 had an average diameter of 44nm and an average length of 6 μm.
In summary, the sizes of the magnetic metal nanowires prepared by the invention all fall into the range of 'diameter of 30-300 nm and length of 1-100 μm', the size range is preferred, the magnetic metal nanowires have good conductivity/magnetic permeability, and the composite material prepared subsequently has good conductivity/magnetic permeability.
(2) The polymer electrospun membranes prepared in examples 4 to 7 were scanned using a scanning electron microscope, and the results are shown in fig. 4 to 7.
As can be seen from FIG. 4, the average diameter of the spun fibers in the polymer electrospun film prepared in example 4 was 0.18 μm, and the thickness was 72 μm.
As can be seen from FIG. 5, the average diameter of the spun fibers in the polymer electrospun film prepared in example 5 was 0.17 μm and the thickness was 90 μm.
As can be seen from FIG. 6, the average diameter of the spun fibers in the polymeric electrospun film prepared in example 6 was 0.16 μm and the thickness was 86 μm.
As can be seen from FIG. 7, the average diameter of the spun fibers in the polymeric electrospun film prepared in example 7 was 0.17 μm and the thickness was 89 μm.
Therefore, the diameter of the spinning fiber in the polymer electrostatic spinning film prepared by the invention is smaller, and the thickness of the polymer electrostatic spinning film is thinner, so that the finally prepared electromagnetic shielding film is thinner, the electromagnetic shielding film has better flexibility, a good electromagnetic shielding effect can be realized under a small volume, and the performance requirements of the current electromagnetic shielding product on thinness, lightness, width and strength are met.
(3) The wave-absorbing composite electromagnetic shielding fiber film prepared in example 4 was scanned by a scanning electron microscope, and the result is shown in fig. 8.
As shown in fig. 8, the nickel nanowires are uniformly loaded on the polymer electrospun membrane formed by the PVDF spun fiber, and the nickel nanowires can subsequently exert good conductivity/magnetic permeability.
(4) The wave-absorbing composite electromagnetic shielding fiber film prepared in example 5 was scanned by a scanning electron microscope, and the result is shown in fig. 9.
As shown in fig. 9, the nickel nanowires are uniformly loaded on the polymer electrospun film formed by the PVDF spun fiber, and the nickel nanowires can subsequently exert good conductivity/magnetic permeability, and the resistivity measured by a four-probe resistivity meter is 1.63 Ω/□.
(5) Scanning the magnetic metal nanowires prepared in the embodiments 4 to 7 by using a scanning electron microscope, wherein the scanning result shows that the nickel nanowire prepared in the embodiment 4 has an average diameter of 48nm and an average length of 14 μm, and the nickel nanowire prepared in the embodiment 5 has an average diameter of 41nm and an average length of 12 μm; the nickel nanowires prepared in example 6 have an average diameter of 48nm and an average length of 14 μm; the nickel nanowires prepared in example 7 averaged 48nm in diameter and 15 μm in length.
(6) The square resistance of the wave-absorbing type composite electromagnetic shielding fiber film prepared in the embodiments 4 to 7 is tested, and through the test, the square resistance of the wave-absorbing type composite electromagnetic shielding fiber film prepared in the embodiment 4 is 0.67 Ω/□, the square resistance of the wave-absorbing type composite electromagnetic shielding fiber film prepared in the embodiment 5 is 1.63 Ω/□, the square resistance of the wave-absorbing type composite electromagnetic shielding fiber film prepared in the embodiment 6 is 1.95 Ω/□, and the square resistance of the wave-absorbing type composite electromagnetic shielding fiber film prepared in the embodiment 7 is 0.89 Ω/□.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A preparation method of a wave-absorbing composite electromagnetic shielding fiber film is characterized by comprising the following steps:
mixing a polymer and an organic solvent, and performing electrostatic spinning on the obtained electrostatic spinning solution to obtain a polymer electrostatic spinning film;
the mass ratio of the polymer to the organic solvent is (5-20) to (80-95);
the voltage of the electrostatic spinning is 8-30 kV;
mixing a solution of soluble metal salt, a solution of a reducing agent, a nucleating agent and a citrate complexing agent, and carrying out reduction reaction in a magnetic field to obtain a metal nanowire stock solution; the soluble metal salt comprises at least one magnetic soluble metal salt; the concentration of the solution of the reducing agent is 0.05-2 mol/L;
and loading the polymer electrostatic spinning film on the metal nanowires in the metal nanowire stock solution to obtain the wave-absorbing composite electromagnetic shielding fiber film.
2. The preparation method according to claim 1, wherein the electrospinning liquid further comprises dielectric nano ceramic powder; the dielectric nano ceramic powder comprises one or more of silicon carbide, silicon nitride, zinc oxide, tin oxide, barium titanate and iron nitride.
3. The preparation method of claim 1, wherein the magnetically soluble metal salt comprises one or more of soluble nickel salt, soluble cobalt salt and soluble iron salt; the reducing agent comprises hydrazine hydrate.
4. The method according to claim 1 or 3, wherein the molar ratio of the soluble metal salt to the reducing agent is 1 (0.5 to 10).
5. The method of claim 1, wherein the nucleating agent comprises chloroplatinic acid.
6. The method of claim 1, wherein the citrate complexing agent comprises sodium citrate.
7. The preparation method according to claim 1, wherein the polymer comprises one or more of polyvinylidene fluoride, polyacrylonitrile, hexafluoropropylene and polyetherimide.
8. The production method according to claim 1 or 7, wherein the organic solvent comprises N, N-dimethylformamide and acetone; the volume ratio of the N, N-dimethylformamide to the acetone is 5 (1-9).
9. The preparation method according to claim 1, wherein the supporting manner comprises one or more of coating, dipping and suction filtration supporting.
10. The wave-absorbing composite electromagnetic shielding fiber film prepared by the preparation method of any one of claims 1 to 9, which comprises a polymer electrostatic spinning film and metal nanowires loaded on the surface and in pores of the polymer electrostatic spinning film, wherein the metal nanowires at least comprise one magnetic metal nanowire.
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