CN113185729A - Flexible silver nanowire transparent electromagnetic shielding film and preparation method thereof - Google Patents
Flexible silver nanowire transparent electromagnetic shielding film and preparation method thereof Download PDFInfo
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- 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 discloses a flexible silver nanowire transparent electromagnetic shielding film, which takes a biological polymer layer as a base film layer, wherein a silver nanowire conducting layer is coated on the base film layer; the silver nanowire conductive layer is coated on the upper surface of the substrate, and the silver nanowire conductive layer is coated on the upper surface of the substrate. The invention also discloses a preparation method of the flexible silver nanowire transparent electromagnetic shielding film. The electromagnetic shielding film adopts the biopolymer film as a base film, and the biopolymer film prepared by taking gelatin as a raw material can be degraded in the environment; because the surface of the biopolymer gelatin film has a large number of oxygen-containing groups, the biopolymer gelatin film can realize a good adhesion effect with the silver nanowire conducting layer without performing additional surface treatment on the biopolymer gelatin film.
Description
Technical Field
The invention relates to an electromagnetic shielding film, in particular to a flexible silver nanowire transparent electromagnetic shielding film and a preparation method of the flexible silver nanowire transparent electromagnetic shielding film.
Background
With the rapid development of electronization and informatization, electronic products grow explosively, and the problems of electromagnetic radiation, electromagnetic interference and the like are inevitably brought while great convenience is provided for daily life and social production life of people. The long-term exposure to the complicated electromagnetic radiation environment greatly influences the normal metabolism of the human body. The electromagnetic waves interfering with each other cause unstable data transmission to high-precision electronic instruments, which is not favorable for obtaining high-quality and high-precision data signals. In addition, the intensive use of various armed devices and precision instruments in the military and aerospace fields causes various electromagnetic waves in the space to interfere with each other, affecting signals for normal operation of the devices and threatening flight safety. In order to meet the application requirements of future electronic equipment such as display screens, intelligent windows and wearable electronic products, the flexible transparent electromagnetic shielding film can meet the requirements of electromagnetic shielding and optical visibility, so that the signal detection and optical observation functions can be guaranteed.
In recent years, a lot of research has been devoted to the development of flexible transparent electromagnetic shielding films, in which the silver nanowire transparent shielding films have excellent overall performance, and thus have attracted the attention of the majority of researchers. For example, Zhengzhou university Shenyu project group (ACS Appl. Mater. interfaces 2020,12,40859-3C2TxAnd silver nanowires. The obtained product can obtain 32dB shielding efficiency in an X wave band, and the light transmittance is 52.3%. Silver nanowires and Fe are loaded on polyethylene terephthalate (PET) base film by using spin coating method (ACS appl. mater. interfaces 2020,12,2826-3O4When the light transmittance of the electromagnetic shielding film is 90%, the electromagnetic shielding effectiveness is 24.9 dB. Most of the flexible transparent electromagnetic shielding films reported at present use PC, PET, etc. as base films. These base films are not degradable in the environment and have adhesion to conductive materialsPoor, it is generally necessary to subject the base film to oxygen plasma treatment or to add a binder to enhance the adhesion between the base film and the conductive material.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems that a base film layer of the transparent electromagnetic shielding film in the prior art cannot be degraded in the environment and has poor adhesion with a conducting layer, the invention provides the flexible silver nanowire transparent electromagnetic shielding film; also provides a preparation method of the flexible silver nanowire transparent electromagnetic shielding film.
The technical scheme is as follows: the flexible silver nanowire transparent electromagnetic shielding film takes a biopolymer layer as a base film layer, and a silver nanowire conducting layer is coated on the base film layer; the silver nanowire conductive layer is characterized by further comprising a biopolymer encapsulating layer, wherein the biopolymer encapsulating layer is coated on the upper surface of the silver nanowire conductive layer.
The surface of the biological polymer film contains a large number of oxygen-containing groups, and can be tightly combined with the silver nanowires without a complex surface pretreatment process; the biological high molecular encapsulation layer is coated on the upper surface of the silver nanowire conducting layer, so that the oxidation of the silver nanowires can be inhibited, and the mechanical property of the electromagnetic shielding film can be enhanced.
Furthermore, according to the flexible silver nanowire transparent electromagnetic shielding film, a large number of oxygen-containing groups on the surface of the biopolymer layer are strongly combined with polyvinylpyrrolidone (PVP) on the surface of the silver nanowire through electrostatic interaction.
The preparation method of the flexible silver nanowire transparent electromagnetic shielding film comprises the following steps:
(1) dispersing the silver nanowires prepared by adopting a polyol method in dispersion liquid to obtain silver nanowire dispersion liquid;
(2) preparing the biopolymer sol: mixing gelatin, plasticizer and water, heating in water bath, stirring until the gelatin is dissolved to form biopolymer sol; heating by a water bath method to be uniformly heated to form a biological polymer film with a smooth surface and no crack;
(3) sequentially coating a biopolymer sol, a silver nanowire dispersion and a biopolymer sol on a substrate; obtaining a sandwich structure of a silver nanowire conducting layer sandwiched between two biological macromolecule layers;
(4) and drying the sandwich structure, and peeling the sandwich structure from the substrate after drying to obtain the flexible silver nanowire transparent electromagnetic shielding film.
Further, in the step (2), the mixing mass ratio of the gelatin to the plasticizer to the water is 5: 1: 50; the water bath heating temperature is 60-62 ℃;
further, in the step (2), the plasticizer is glycerol, and the water is deionized water.
Further, in the step (3), the areal density of the silver nanowires in the silver nanowire layer is 111.1-250.0 mg/m2；
Further, in the step (4), the drying temperature is not lower than 25 ℃.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
firstly, the electromagnetic shielding film adopts a biological polymer film as a base film, and the biological polymer film prepared by taking gelatin as a raw material can realize degradation in the environment, such as thermocatalytic degradation, wherein the degradation condition is 121 ℃, and the period is 2 hours;
secondly, because the surface of the biopolymer gelatin film has a large number of oxygen-containing groups, the biopolymer gelatin film can realize good adhesion effect with the silver nanowire conducting layer without additional surface treatment;
thirdly, the peptide chain of the gelatin and water form a stable three-dimensional network structure through hydrogen bonds, the gelatin film is dried and dehydrated to form a film, glycerin is used as a plasticizer to enter the molecular chain of the gelatin, and intermolecular force is weakened through prolonging the molecular chain, so that the flexibility of the gelatin film is improved;
finally, because the silver nanowires are dispersed in water and coated on the biopolymer substrate layer and then dried, in the drying process, water is condensed near the silver nanowire junctions and fills gaps among the junctions, and water is evaporated to a certain degree in the drying process, a meniscus-shaped liquid bridge is formed among the nanowires, so that attraction is generated, the separated silver nanowires are mutually contacted and crossed to form a conductive network, and under the action of capillary tubes, the silver nanowire intersections are deformed, the wires are tightly contacted with one another, so that the contact resistance of the wires is reduced, and the lower the resistance of the conductive layer is, the better the shielding performance of the material is.
Drawings
FIG. 1 is a Fourier infrared transform spectrum of a biopolymer membrane layer of the present invention;
FIG. 2 is a SEM image of a biopolymer membrane layer according to the present invention;
fig. 3 is an SEM picture of the flexible silver nanowire transparent electromagnetic shielding film manufactured in example 1 of the present invention;
fig. 4 is a sectional SEM picture of the flexible silver nanowire transparent electromagnetic shielding film manufactured in example 6 of the present invention;
fig. 5 is a light transmittance diagram of the flexible silver nanowire transparent electromagnetic shielding films manufactured in examples 1, 2, 3, 4, 5, and 6 of the present invention;
fig. 6 is a conductivity test chart of the flexible silver nanowire transparent electromagnetic shielding thin film manufactured in examples 1, 2, 3, 4, 5, and 6 of the present invention;
fig. 7 is an electromagnetic shielding performance test chart of the flexible silver nanowire transparent electromagnetic shielding films manufactured in embodiments 1, 2, 3, 4, 5, and 6 of the present invention;
fig. 8 is a drawing test chart of the flexible silver nanowire transparent electromagnetic shielding films manufactured in examples 1, 2, 3, 4, 5, and 6 of the present invention;
fig. 9 is a bending resistance test chart of the flexible silver nanowire transparent electromagnetic shielding film manufactured in example 6 of the present invention;
fig. 10 is a process diagram of the flexible silver nanowire transparent electromagnetic shielding film according to the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The preparation method of the flexible silver nanowire transparent electromagnetic shielding film comprises the following steps:
(1) preparing silver nanowires by a polyol method: mixing 1.6g polyvinylpyrrolidone with average molecular weight of 1300000 and 50mL ethylene glycol, stirring to dissolve, adding 20.5mmol/L1.6mL of NaCl solution to form solution A; 0.54g of AgNO3Mixing with 30mL of glycol, stirring and dissolving to form a solution B; dropwise adding the solution A into the solution B to form a solution C, uniformly stirring, and transferring to a reaction kettle for hydrothermal reaction at 160 ℃ for 7 hours; after the reaction is finished, cleaning the silver nanowire by using ethanol, acetone and deionized water, centrifuging and collecting the silver nanowire, and dispersing the obtained silver nanowire into the deionized water to obtain silver nanowire dispersion liquid;
(2) preparing the biopolymer sol: gelatin, glycerol and deionized water are mixed in a mass ratio of 5: 1: mixing the materials at 50 ℃, heating the mixture in water bath at 60 ℃ and stirring the mixture until the gelatin is dissolved to form biopolymer sol;
(3) preparing the flexible silver nanowire transparent electromagnetic shielding film: sequentially blade-coating a biopolymer sol, a silver nanowire dispersion solution and a biopolymer sol on a clean glass substrate to obtain a sandwich structure in which a silver nanowire conducting layer is sandwiched between two biopolymer layers; the surface density of the silver nanowires in the silver nanowire conducting layer is 111.1mg/m2；
(4) And (3) drying at 25 ℃, and peeling the interlayer film from the glass substrate to obtain the flexible silver nanowire transparent electromagnetic shielding film.
Example 2
The areal density of the silver nanowires in step (3) of example 1 was prepared to be 138.9mg/m2And other conditions of the prepared film are unchanged, so that the flexible silver nanowire transparent electromagnetic shielding film is obtained.
Example 3
The areal density of the silver nanowires in step (3) of example 1 was prepared to be 166.7mg/m2And other conditions of the prepared film are unchanged, so that the flexible silver nanowire transparent electromagnetic shielding film is obtained.
Example 4
The areal density of the silver nanowires in step (3) of example 1 was prepared to be 194.4mg/m2And other conditions of the prepared film are unchanged, so that the flexible silver nanowire transparent electromagnetic shielding film is obtained.
Example 5
The areal density of the silver nanowires in step (3) of example 1 was prepared to be 222.2mg/m2And other conditions of the prepared film are unchanged, so that the flexible silver nanowire transparent electromagnetic shielding film is obtained.
Example 6
The silver nanowire areal density in step (3) of example 1 was prepared to be 250.0mg/m2And other conditions of the prepared film are unchanged, so that the flexible silver nanowire transparent electromagnetic shielding film is obtained.
Comparative example 1
(1) Preparing silver nanowires by a polyol method: mixing 1.6g of polyvinylpyrrolidone with the average molecular weight of 1300000 and 50mL of ethylene glycol, stirring to dissolve, and adding 1.6mL of NaCl solution with the concentration of 20.5mmol/L to form solution A; 0.54g of AgNO3Mixing with 30mL of glycol, stirring and dissolving to form a solution B; dropwise adding the solution A into the solution B to form a solution C, uniformly stirring, and transferring to a reaction kettle for hydrothermal reaction at 160 ℃ for 7 hours; after the reaction is finished, cleaning the silver nanowire by using ethanol, acetone and deionized water, centrifuging and collecting the silver nanowire, and dispersing the obtained silver nanowire into the ethanol to obtain silver nanowire dispersion liquid;
(2) preparing the biopolymer sol: gelatin, glycerol and deionized water are mixed in a mass ratio of 5: 1: mixing the materials at 50 ℃, heating the mixture in water bath at 60 ℃ and stirring the mixture until the gelatin is dissolved to form biopolymer sol;
(3) preparing the flexible silver nanowire transparent electromagnetic shielding film: sequentially blade-coating a biopolymer sol, a silver nanowire dispersion solution and a biopolymer sol on a clean glass substrate to obtain a sandwich structure in which a silver nanowire conducting layer is sandwiched between two biopolymer layers; the surface density of the silver nanowires in the silver nanowire conducting layer is 111.1mg/m2；
(4) And (3) drying at 25 ℃, and peeling the interlayer film from the glass substrate to obtain the flexible silver nanowire transparent electromagnetic shielding film.
FIG. 1 shows a Fourier transform infrared spectrum of a biopolymer layer according to the invention, as seen in FIG. 1 at 3285.6cm-1The amide A band appears, which is caused by the stretching vibration of the N-H group. The amide B band is located at 2933.7cm-1Here, this is caused by the stretching vibration of the C-H group. Amide I, II bands at 1629.1, 1542And 7, respectively, the stretching vibration of C ═ O and the-COO, N-H bending vibration and C-N stretching vibration which are hydrogen bonded. Amide III bands at 1236.6cm-1In-plane vibration of the C-N and N-H groups and-CH from the side chains of glycerol and hydroxyproline2The radicals are generated. Located at 1034.6cm-1The nearby peaks are related to the stretching vibration of the C-O group. Fourier infrared transform spectrum proves that the surface of the biopolymer membrane prepared by the invention has a large amount of oxygen-containing groups, and the biopolymer membrane can be tightly combined with the silver nanowires without pretreatment.
FIG. 2 is a SEM picture of the biopolymer membrane layer of the present invention, and it can be seen from FIG. 2 that the biopolymer membrane has a smooth and non-cracked surface. Fig. 3 is an SEM picture of the flexible silver nanowire transparent electromagnetic shielding film prepared in example 1, and it can be seen from fig. 3 that silver nanowires are crossed to form a conductive network, and under the action of capillary, the crossing points of the silver nanowires are deformed, and the resistance of the conductive layer is reduced after the wires are tightly contacted with each other, so that the electromagnetic shielding performance is improved. Most incident electromagnetic waves are reflected out on the surface of the material due to impedance mismatch, and the rest incident electromagnetic waves enter the material, interact with current carriers on the surface of the conductive layer to generate induced current, and the electromagnetic wave energy is converted into heat energy, so that the material has good electromagnetic wave shielding capability. Fig. 4 is a SEM picture of a cross-section of the flexible silver nanowire transparent electromagnetic shielding thin film prepared in example 6, and it can be seen from fig. 4 that the silver nanowire layer is fixed between the biopolymer base film and the encapsulation layer to form a sandwich structure.
Fig. 5 is a graph of light transmittance of the flexible silver nanowire transparent electromagnetic shielding films manufactured in examples 1, 2, 3, 4, 5, and 6, and it can be seen from fig. 5 that as the areal density of the silver nanowires increases, the light transmittance of the electromagnetic shielding films decreases, and the light transmittance at 550nm is 89.6, 86.7, 82.4, 79.7, 75.9, and 72.0%, respectively.
Fig. 6 is a conductivity test chart of the flexible silver nanowire transparent electromagnetic shielding films prepared in examples 1, 2, 3, 4, 5 and 6, and it can be seen from fig. 6 that the sheet resistance decreases with the increase of the areal density of the silver nanowires, which shows that the conductivity of the electromagnetic shielding film increases with the increase of the areal density of the silver nanowires.
Fig. 7 is an electromagnetic shielding performance test chart of the flexible silver nanowire transparent electromagnetic shielding films manufactured in embodiments 1, 2, 3, 4, 5, and 6, and it can be seen from fig. 7 that in the X-band (8.2 to 12.4GHz), as the areal density of the silver nanowires increases, the electromagnetic shielding effectiveness increases, and the electromagnetic shielding effectiveness at 8.2GHz is sequentially 8.83, 12.60, 16.68, 20.94, 30.07, and 37.74 dB.
Fig. 8 is a tensile test chart of the flexible silver nanowire transparent electromagnetic shielding films prepared in examples 1, 2, 3, 4, 5, and 6, and it can be seen from fig. 8 that the tensile strength of the flexible silver nanowire transparent electromagnetic shielding film using biomacromolecule sol as a base film and an encapsulation layer is not greatly affected by the areal density of the silver nanowires, when the thickness is 17 μm, the tensile strength is between 50 MPa and 55MPa, and the elongation at break increases with the increase of the areal density of the silver nanowires; in comparative example 1, when ethanol was used as the dispersion, the sheet resistance of the prepared composite film was 99.8 Ω/sq, and the difference in conductivity from the electromagnetic shielding film prepared by the present invention was small; but the tensile strength of the prepared composite membrane is only 35.17Mpa, and the elongation at break is 2.46%; the tensile strength is far lower than that of the electromagnetic shielding film prepared by the invention, and the gelatin is denatured by ethanol, so that the obtained electromagnetic shielding film becomes brittle and has weak flexibility and poor mechanical property.
Fig. 9 is a bending resistance test chart of the flexible silver nanowire transparent electromagnetic shielding film prepared in example 6, and it can be seen from fig. 9 that the electromagnetic shielding performance of the flexible silver nanowire transparent electromagnetic shielding film is not changed much after the flexible silver nanowire transparent electromagnetic shielding film is bent 1000 times, which shows that the flexible silver nanowire transparent electromagnetic shielding film provided by the present invention has good durability and good flexibility.
The flexible silver nanowire transparent electromagnetic shielding film prepared by the invention can realize degradation in the environment by adopting the biological polymer film as the base film and the biological polymer film prepared by taking gelatin as the raw material; a large number of oxygen-containing groups on the surface of the gelatin film can realize a good adhesion effect with the silver nanowire conducting layer, glycerin is combined to be used as a plasticizer to enter a gelatin molecular chain, intermolecular force is weakened by prolonging the molecular chain, and the effect that the flexible silver nanowire transparent electromagnetic shielding film has excellent flexibility is achieved; meanwhile, the silver nanowires are crossed to form a conductive network in the preparation process, and the resistance and the material shielding performance of the conductive layer are high; the biological polymer film has a synergistic protection effect on the silver nanowire conducting layer, and the durability of the flexible silver nanowire transparent electromagnetic shielding film is greatly improved.
Claims (7)
1. The utility model provides a transparent electromagnetic shield film of flexible silver nano-wire which characterized in that: the flexible silver nanowire transparent shielding film takes a biological polymer layer as a base film layer, and a silver nanowire conducting layer is coated on the base film layer; the silver nanowire conductive layer is characterized by further comprising a biopolymer encapsulating layer, wherein the biopolymer encapsulating layer is coated on the upper surface of the silver nanowire conductive layer.
2. The flexible silver nanowire transparent electromagnetic shielding film of claim 1, wherein: the biological macromolecule layer is connected with the silver nanowire conducting layer through electrostatic interaction.
3. A method for preparing the flexible silver nanowire transparent electromagnetic shielding film according to claim 1, comprising the following steps:
(1) dispersing the silver nanowires prepared by adopting a polyol method in dispersion liquid to obtain silver nanowire dispersion liquid;
(2) preparing the biopolymer sol: mixing gelatin, plasticizer and water, and stirring under water bath heating condition until the gelatin is dissolved to form biopolymer sol;
(3) sequentially coating a biopolymer sol, a silver nanowire dispersion and a biopolymer sol on a substrate; obtaining a sandwich structure of a silver nanowire conducting layer sandwiched between two biological macromolecule layers;
(4) and drying the sandwich structure, and peeling the sandwich structure from the substrate after drying to obtain the flexible silver nanowire transparent electromagnetic shielding film.
4. The method for preparing the flexible silver nanowire transparent electromagnetic shielding film according to claim 3, wherein the flexible silver nanowire transparent electromagnetic shielding film is prepared by a method comprising a step of coating a surface of a substrate with a solution of a solventIn the following steps: in the step (3), the surface density of the silver nanowires in the silver nanowire conducting layer is 111.1-250.0 mg/m2。
5. The method for preparing the flexible silver nanowire transparent electromagnetic shielding film according to claim 3, wherein the method comprises the following steps: in the step (2), the mixing mass ratio of the gelatin to the plasticizer to the water is 5: 1: 50; the water bath heating temperature is 60-62 ℃.
6. The method for preparing the flexible silver nanowire transparent electromagnetic shielding film according to claim 3, wherein the method comprises the following steps: in the step (2), the plasticizer is glycerol.
7. The method for preparing the flexible silver nanowire transparent electromagnetic shielding film according to claim 3, wherein the method comprises the following steps: in the step (4), the drying temperature is not lower than 25 ℃.
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| CN103834050A (en) * | 2014-03-21 | 2014-06-04 | 北京科技大学 | Method for preparing gelatin/nano-silver/chitosan derivative composite film |
| CN106024099A (en) * | 2016-05-30 | 2016-10-12 | 兰州大学 | Preparation method of flexible transparent conductive thin film of electrospun silver nanofiber network |
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| CN103834050A (en) * | 2014-03-21 | 2014-06-04 | 北京科技大学 | Method for preparing gelatin/nano-silver/chitosan derivative composite film |
| CN106024099A (en) * | 2016-05-30 | 2016-10-12 | 兰州大学 | Preparation method of flexible transparent conductive thin film of electrospun silver nanofiber network |
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