CN115181388B - Stretchable electromagnetic shielding elastic material and preparation method thereof - Google Patents
Stretchable electromagnetic shielding elastic material and preparation method thereof Download PDFInfo
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- 239000013013 elastic material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- BKLFJQMYGDQCPM-UHFFFAOYSA-N C(=C)C1=C(C=CC=C1)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C(=C)C1=C(C=CC=C1)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 BKLFJQMYGDQCPM-UHFFFAOYSA-N 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
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- 230000009471 action Effects 0.000 description 1
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- QLIWBTIDJYVPMM-UHFFFAOYSA-M silver ethanol 2,2,2-trifluoroacetate Chemical compound CCO.C(=O)(C(F)(F)F)[O-].[Ag+] QLIWBTIDJYVPMM-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention discloses a stretchable electromagnetic shielding elastic material and a preparation method thereof. The stretchable electromagnetic shielding elastomeric material comprises a thermoplastic elastomer polymer, a fibrous carbon filler and silver nanoparticles; the stretchable electromagnetic shielding elastic material is provided with a thermoplastic elastomer polymer substrate containing fibrous carbon fillers, and the surface and the inside of the substrate are provided with embedded silver nano particles; wherein the mass fraction of the thermoplastic elastomer polymer in the stretchable electromagnetic shielding elastic material is 40-60%, the mass fraction of the fibrous carbon filler in the stretchable electromagnetic shielding elastic material is 2-10%, and the mass fraction of the silver nano particles in the stretchable electromagnetic shielding elastic material is 30-58%. The preparation method is simple, has excellent electromagnetic shielding performance and good stretching stability, and has wide prospect in the emerging fields of electronic devices, flexible wearable electronics, electronic skin and the like.
Description
Technical Field
The invention relates to a stretchable flexible electromagnetic shielding material compounded by silver nano particles, fibrous carbon fillers and thermoplastic elastomer polymers and a preparation method thereof.
Background
The electronic information industry is an important driving force for keeping industrial economy in China to be sustainable, and along with the development of information technology, electronic equipment and communication technology are continuously improved, and various electromagnetic interference pollution problems are increasingly highlighted. On the one hand, electromagnetic interference may cause other electronic devices or equipment to malfunction or even malfunction; on the other hand, electromagnetic pollution may have a certain influence on the health. Therefore, research on high-performance electromagnetic interference shielding materials is of great importance.
In recent decades, various metals and alloys thereof have been widely used in the field of electromagnetic shielding, but the requirements of miniaturization, light weight and flexibility of electronic equipment at present cannot be met due to the defects of high density, high price, poor corrosion resistance, difficulty in bending and the like, although the electromagnetic shielding performance is excellent. In recent years, electromagnetic shielding composite materials mainly based on polymer-based conductive composite materials are increasingly focused by researchers, and compared with traditional metal shielding materials, the materials have the advantages of low density, low cost, easy processing, corrosion resistance, good flexibility and the like, and have wide application prospects.
In particular, the rise of flexible electronic devices places higher demands on the flexibility and stability of electromagnetic shielding materials. On one hand, the electromagnetic shielding material in the flexible electronic equipment needs to still maintain the electromagnetic shielding capability under a certain range of deformation; on the other hand, the flexible electronic device may be bent and worn during use to damage the structure of the electromagnetic shielding material, so that it needs to have better durability and stability. For the filled composite electromagnetic shielding composite material, conductive substances are filled in the polymer matrix, so that the stability is better, but the mechanical properties (flexibility) of the composite material are affected to a certain extent by the conductive filler; for the surface conductive electromagnetic shielding composite material, conductive substances are usually attached to the surface layer of the polymer, so that the mechanical property (flexibility) of the polymer matrix is not obviously affected, but the stability of the surface conductive layer is poor, and the surface conductive layer is easy to break or separate. Therefore, how to enhance the conductivity stability of the electromagnetic shielding composite material without affecting the flexibility thereof is a major concern at present.
Disclosure of Invention
In order to solve the problems, the invention provides a stretchable electromagnetic shielding elastic material and a preparation method thereof. According to the invention, a styrene thermoplastic elastomer polymer is used as a matrix, fibrous carbon fillers and silver nano particles are respectively used as conductive fillers, the fibrous carbon fillers/thermoplastic elastomer polymer is prepared by a solution pouring drying method, and nano silver particles are grown on the upper surface and the lower surface of the polymer matrix and the inner layer of the polymer matrix by a swelling adsorption and in-situ reduction method, so that the stretchable electromagnetic shielding elastic material compounded by the silver nano particles/fibrous carbon fillers/thermoplastic elastomer polymer is prepared.
In one aspect, the present invention provides a stretchable electromagnetic shielding elastomeric material comprising a thermoplastic elastomeric polymer, a fibrous carbon filler, and silver nanoparticles; the stretchable electromagnetic shielding elastic material is provided with a thermoplastic elastomer polymer substrate containing fibrous carbon fillers, and the surface and the inside of the substrate are provided with embedded silver nano particles; wherein the mass fraction of the thermoplastic elastomer polymer in the stretchable electromagnetic shielding elastic material is 40-60%, the mass fraction of the fibrous carbon filler in the stretchable electromagnetic shielding elastic material is 2-10%, and the mass fraction of the silver nano particles in the stretchable electromagnetic shielding elastic material is 30-58%.
Further, the thermoplastic elastomeric polymer is selected from the group consisting of styrenic elastomeric materials, preferably at least one of styrene-divinylbenzene-styrene block copolymers, styrene-butadiene-styrene block copolymers SBS, hydrogenated styrene-butadiene-styrene block copolymers SEBS, styrene-butadiene-styrene block copolymers SIS, styrene-ethylene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated styrene isoprene copolymers, and modified or grafted elastomers thereof.
Further, the fibrous carbon filler is selected from the group consisting of carbon nanofibers, carbon nanotubes, and carbon fibers. Preferably, the fibrous carbon filler has an aspect ratio of 5 to 5000.
Further, the mass fraction of the thermoplastic elastomer polymer in the stretchable electromagnetic shielding elastic material is 40% -46%, the mass fraction of the fibrous carbon filler in the stretchable electromagnetic shielding elastic material is 4% -8%, and the mass fraction of the silver nano particles in the stretchable electromagnetic shielding elastic material is 50% -55%.
Further, the stretchable electromagnetic shielding elastic material is a layered material, preferably having a thickness of 200 μm to 10mm.
Further, the thermoplastic elastomeric polymer is non-foamed.
Further, the stretchable electromagnetic shielding elastomeric material comprises silver nanoparticles in the thermoplastic elastomeric polymer in a depth range of 0-120 μm from the surface; more preferably in the depth range of 0-100 μm.
In another aspect, the present invention provides a method for preparing the stretchable electromagnetic shielding elastic material, which comprises the following steps:
(1) Preparing a thermoplastic elastomer polymer solution and a fibrous carbon filler dispersion: respectively dissolving a thermoplastic elastomer polymer and a fibrous carbon filler in an organic solvent, uniformly mixing to obtain a thermoplastic elastomer polymer solution and a fibrous carbon filler dispersion,
(2) Preparing a fibrous carbon filler and thermoplastic elastomer polymer mixed solution: mixing the fibrous carbon filler dispersion liquid with the thermoplastic elastomer polymer solution until the fibrous carbon filler is uniformly dispersed in the mixed solution to obtain a fibrous carbon filler and thermoplastic elastomer polymer mixed solution;
(3) Pouring and drying: pouring the fibrous carbon filler/thermoplastic elastomer polymer solution obtained in the step (2) into a mold, and drying to obtain a fibrous carbon filler and thermoplastic elastomer polymer composite material;
(4) Preparing silver salt solution: mixing silver salt with an organic solvent to obtain silver salt solution,
(5) Adsorption of silver trifluoroacetate: immersing the fibrous carbon filler and thermoplastic elastomer polymer composite material obtained in the step (3) into the silver salt solution obtained in the step (4), taking out and drying to obtain the fibrous carbon filler and thermoplastic elastomer polymer composite material adsorbed with silver salt;
(6) And (3) reduction: immersing the fibrous carbon filler and thermoplastic elastomer polymer composite material with silver salt adsorbed on the surface obtained in the step (5) into a reducing agent solution for reduction, taking out, cleaning and drying to obtain the silver nanoparticle/fibrous carbon filler/thermoplastic elastomer polymer composite stretchable flexible electromagnetic shielding material.
Further, in the step (1), the organic solvent is selected from one or more of aromatic solvents, esters solvents and ketone solvents,
further, in the step (1), the organic solvent is selected from any one or more of dioxane, toluene, xylene, ethyl acetate and isophorone;
further, in step (1), the mass ratio of the fibrous carbon filler to the solvent is 1: 19-3: 17, the mass ratio of the thermoplastic elastomer polymer to the solvent mixture is 1: 9-1: 5,
further, in the step (1), the thermoplastic elastomer polymer and the fibrous carbon filler are dissolved in a solvent, and the thermoplastic elastomer polymer is completely dissolved and the fibrous carbon filler is uniformly dispersed by mechanical force;
further, in the step (2), the fibrous carbon filler dispersion liquid is mixed with the polymer solution, and the mixture is magnetically stirred for 6 hours to obtain a carbon fiber/thermoplastic elastomer polymer solution which is uniformly dispersed;
further, the raw materials after the fibrous carbon filler dispersion liquid and the polymer solution in the step (2) are mixed comprise 85-95% of polymer and 5-15% of carbon fiber by mass percent;
further, in the step (3), the drying is performed by adopting a heating mode or a negative pressure mode.
Further, the heating temperature in the step (3) is 60-100 ℃ and the heating time is 6-12 h.
Further, the silver salt in step (4) is selected from silver trifluoroacetate.
Further, the mass fraction of silver salt in the silver salt solution in the step (4) is 5% -20%.
Further, the reducing agent solvent in the step (5) is selected from hydrazine hydrate solution, and the concentration of the reducing agent solvent is 50%.
In yet another aspect, the present invention provides the use of a stretchable electromagnetic shielding elastomeric material as an electromagnetic shielding material in the manufacture of an electronic product.
The stretchable electromagnetic shielding elastic material and the preparation method thereof provided by the invention have the following advantages:
1. the styrenic elastomer material has a large elongation and good rebound resilience, and by adding fibrous carbon fillers, higher conductivity at low loading can be achieved while maintaining a large elongation.
2. The styrene elastomer and the silver trifluoroacetate ethanol solution have unique ion-dipole interaction, silver nano particles can be realized on the surface of the styrene elastomer and the inner layer thereof after adsorption reduction, the interface binding force between the nano silver particles and a polymer matrix is greatly improved, and the problems that a metal layer prepared by the traditional chemical plating, electroplating and other methods has weak binding force with the polymer matrix and is easy to fall off are avoided. And the embedded metal structure is not easy to crack under the action of external forces such as stretching, bending, folding, winding, twisting and the like, so that the force-guiding performance is more stable, and the electromagnetic shielding performance is more excellent.
3. The fibrous carbon filler in the stretchable electromagnetic shielding elastic material can promote the growth of silver nano particles in the polymer matrix, and improve the overall conductivity of the composite material. In addition, the composite material contains carbon material with high length-diameter ratio and granular nano silver as conductive phase, and can form a more abundant and effective conductive network inside the polymer matrix, so that the conductivity and electromagnetic shielding performance of the composite material can be improved, and the composite material has excellent force-electric stability.
Drawings
Fig. 1 is a schematic structural view of a silver nanoparticle/fibrous carbon filler/elastomer polymer composite material according to the present invention and a schematic structural view of a comparative example, wherein the left side is a schematic view of the stretchable electromagnetic shielding elastic material according to the present invention, and compared with the right side, for example, a comparative example not including the fibrous carbon filler, the silver nanoparticle obtained by reduction can be more deeply embedded into the inside of the elastomer polymer due to the fibrous carbon filler added to the elastomer polymer.
Fig. 2 is an SEM image of a cross section of a silver nanoparticle/carbon nanofiber/styrene-divinylbenzene-styrene block copolymer composite.
Fig. 3 is a surface SEM image of the silver nanoparticle/carbon nanofiber/styrene-divinylbenzene-styrene block copolymer composite in a stretched state.
Fig. 4 is a graph showing the mechanical and electrical synchronization of a silver nanoparticle/carbon nanofiber/styrene-divinylbenzene-styrene block copolymer composite.
Fig. 5 is a graph showing the variation of electromagnetic shielding effectiveness of a silver nanoparticle/carbon nanofiber/styrene-divinylbenzene-styrene block copolymer composite in different elongation conditions.
Fig. 6 is a cross-sectional SEM image of silver nanoparticle/styrene-divinylbenzene-styrene block copolymer composites.
Fig. 7 is a graph showing the variation of electromagnetic shielding effectiveness of silver nanoparticle/styrene-divinylbenzene-styrene block copolymer composites under different elongation conditions.
Fig. 8 is a cross-sectional SEM image of a carbon nanofiber/styrene-divinylbenzene-styrene block copolymer composite.
Fig. 9 is a graph showing the variation of electromagnetic shielding effectiveness of the carbon nanofiber/styrene-divinylbenzene-styrene block copolymer composite in different tensile ratios.
Detailed Description
Example 1
Firstly, adding carbon nanofiber and a styrene-butadiene-styrene block copolymer into isophorone respectively to prepare a carbon nanofiber dispersion liquid with the mass fraction of 5wt% and a styrene-butadiene-styrene block copolymer solution with the mass fraction of 15wt%, carrying out ultrasonic treatment for 30min in an ultrasonic cytoclasis instrument and magnetically stirring for 12h until the polymer is completely dissolved and the carbon nanofiber is uniformly dispersed. Then, the carbon nanofiber dispersion liquid is mixed with a styrene-butadiene-styrene block copolymer solution to prepare a mass ratio of the carbon nanofiber to the styrene-butadiene-styrene block copolymer of 1:9, and magnetically stirring the mixed solution for 6 hours until the carbon nanofibers are uniformly dispersed in the solution. And pouring the obtained mixed solution into a mould, and drying for 12 hours in a blowing drying box at 80 ℃ to obtain the carbon nanofiber/styrene-butadiene-styrene block copolymer composite material. Adding the silver trifluoroacetate powder into ethanol, and magnetically stirring for 10min until the silver trifluoroacetate is completely dissolved to obtain a silver trifluoroacetate solution with the mass fraction of the silver trifluoroacetate of 15 wt%. Then soaking the carbon nanofiber/styrene-butadiene-styrene block copolymer composite material in a silver trifluoroacetate solution for 30min, taking out and drying; and completely immersing the dried composite material in 98% hydrazine hydrate solution for 30min, taking out, cleaning and drying to obtain the stretchable electromagnetic shielding elastic material of the silver nano particles/carbon nano fibers/thermoplastic elastomer polymer.
The cross-sectional structure is shown in the electron microscope figure 2. The stretchable electromagnetic shielding elastic material is seen through the interface to have light-colored thin layers on both sides, which are silver nanoparticle layers formed on the outer surface, and carbon nanofibers within the inner copolymer, and silver nanoparticles around the carbon nanofibers. It was demonstrated that the formation of silver nanoparticles inside the copolymer was improved by the addition of carbon nanofibers.
As is apparent from comparison of fig. 2 and 6 (the cross-sectional view of comparative example 1, i.e., the composite material without carbon nanofibers added), the penetration depth of the silver nanoparticles into the polymer substrate was shallow, about 20 to 30 μm, without carbon nanofibers added, whereas the penetration of the silver nanoparticles into the polymer substrate was significantly deepened, about 100 μm, in the adsorption-reduction sample after carbon nanofibers were added. As can be seen in connection with fig. 4-5 and 7, the deeper embedded structure of silver nanoparticles provides the advantage that the overall conductivity (electromagnetic shielding properties) of the material is better and the conductivity retention during stretching is better (relatively less attenuation of conductivity during stretching).
Example 2
Adding carbon nanofiber and styrene-butadiene-styrene block copolymer into isophorone respectively to prepare a carbon nanofiber dispersion liquid with the mass fraction of 5wt% and a styrene-butadiene-styrene block copolymer solution with the mass fraction of 15wt%, carrying out ultrasonic treatment for 1h in an ultrasonic cell disruption instrument and magnetically stirring for 6h until the polymer is completely dissolved and the carbon nanofiber is uniformly dispersed. Mixing the carbon nanofiber dispersion liquid with a styrene-butadiene-styrene block copolymer solution to prepare a carbon nanofiber and styrene-butadiene-styrene block copolymer with the mass ratio of 3:17, magnetically stirring the solution for 6 hours until the carbon nanofibers are uniformly dispersed in the solution; pouring the obtained mixed solution into a mould, and drying for 12 hours in a blowing drying box at 80 ℃ to obtain the carbon nanofiber/styrene-butadiene-styrene block copolymer composite material. Adding the silver trifluoroacetate powder into ethanol, and magnetically stirring for 10min until the silver trifluoroacetate is completely dissolved to obtain a silver trifluoroacetate solution with the mass fraction of 20wt% of the silver trifluoroacetate. Then soaking the carbon nanofiber/styrene-butadiene-styrene block copolymer composite material in a silver trifluoroacetate solution for 30min, taking out and drying; and (3) completely immersing the dried composite material in a 50% hydrazine hydrate solution for 30min, taking out, cleaning and drying to obtain the stretchable electromagnetic shielding elastic material of the silver nano particles/carbon fibers/thermoplastic elastomer polymer. The surface topography in the stretched state is shown in FIG. 3.
It can be seen from fig. 3 that the carbon material having a fibrous shape inside the copolymer achieves higher conductivity during stretching. Silver nanoparticles on the surface of the copolymer, as well as silver nanoparticles embedded in the inner layer of the copolymer, can also be observed. The surface and internal silver nanoparticles are firmly combined during the stretching process.
Example 3
Adding carbon nanofiber and styrene-butadiene-styrene block copolymer into isophorone respectively to prepare carbon nanofiber dispersion liquid with the mass fraction of 3wt% and styrene-butadiene-styrene block copolymer solution with the mass fraction of 20wt%, performing ultrasonic treatment in an ultrasonic cell disruption instrument for 30min and magnetically stirring for 12h until the polymer is completely dissolved and the carbon nanofiber is uniformly dispersed; mixing the carbon nanofiber dispersion liquid with a styrene-butadiene-styrene block copolymer solution to prepare a carbon nanofiber and styrene-butadiene-styrene block copolymer with the mass ratio of 3:17, magnetically stirring the solution for 6 hours until the carbon nanofibers are uniformly dispersed in the solution; pouring the obtained mixed solution into a mould, and drying for 12 hours in a blowing drying oven at 80 ℃ to obtain a carbon nanofiber/styrene-butadiene-styrene block copolymer composite material; dissolving silver trifluoroacetate in ethanol, and magnetically stirring for 10min until the silver trifluoroacetate is completely dissolved to obtain a silver trifluoroacetate solution with the mass fraction of 15 wt%; soaking the carbon nanofiber/styrene-butadiene-styrene block copolymer composite material in a silver trifluoroacetate solution for 30min, taking out and drying; and (3) completely immersing the dried composite material in 50% hydrazine hydrate solution, immersing and reducing for 30min, taking out, cleaning and drying to obtain the stretchable electromagnetic shielding elastic material of the silver nano particles/carbon fibers/thermoplastic elastomer polymer. It was cut into a long strip shape, and was subjected to a tensile test using an universal tester for mechanics, and the resistance change during the tensile process thereof was measured simultaneously using an electronic multimeter, as shown in fig. 4. Fig. 4 shows force-electricity synchronous test data, namely the mechanical change and the electrical change rule of the test material in the stretching process. The test results show that the resistance value of the material of the invention is still kept at a very low level in the stretching process, in other words, the material still has good conductive performance (electromagnetic shielding performance) under high tensile strain.
Example 4
Adding carbon nanofiber and styrene-butadiene-styrene block copolymer into isophorone respectively to prepare a carbon nanofiber dispersion liquid with the mass fraction of 5wt% and a styrene-butadiene-styrene block copolymer solution with the mass fraction of 15wt%, carrying out ultrasonic treatment in an ultrasonic cell disruption instrument for 30min and magnetically stirring for 12h until the polymer is completely dissolved and the carbon nanofiber is uniformly dispersed; mixing the carbon nanofiber dispersion liquid with a styrene-butadiene-styrene block copolymer solution to prepare a carbon nanofiber and styrene-butadiene-styrene block copolymer with the mass ratio of 3:17, magnetically stirring the solution for 6 hours until the carbon nanofibers are uniformly dispersed in the solution; pouring the obtained mixed solution into a mould, and drying for 12 hours in a blowing drying oven at 80 ℃ to obtain a carbon nanofiber/styrene-butadiene-styrene block copolymer composite material; dissolving silver trifluoroacetate in ethanol, and magnetically stirring for 10min until the silver trifluoroacetate is completely dissolved to obtain a silver trifluoroacetate solution with the mass fraction of 15 wt%; soaking the carbon nanofiber/styrene-butadiene-styrene block copolymer composite material in a silver trifluoroacetate solution for 30min, taking out and drying; and (3) completely immersing the dried composite material in a 50% hydrazine hydrate solution for 30min, taking out, cleaning and drying to obtain the stretchable electromagnetic shielding elastic material of the silver nano particles/carbon fibers/thermoplastic elastomer polymer. The electromagnetic shielding performance of the composite material in different stretching states is tested by adopting a waveguide network analyzer, as shown in fig. 5, the initial electromagnetic shielding performance of the composite material is 103dB (X-band, 8.2-12.4 GHz), and the composite material still has the electromagnetic shielding performance of 33.4dB under 100% stretching strain.
Comparative example 1
Adding the styrene-butadiene-styrene block copolymer into isophorone, stirring and fully dissolving to prepare a solution with the mass fraction of 15wt%, pouring the solution into a mould, and drying the solution in a blast drying oven at 80 ℃ for 12 hours to obtain the styrene-butadiene-styrene block copolymer sheet. Adding the silver trifluoroacetate powder into ethanol, and magnetically stirring for 10min until the silver trifluoroacetate is completely dissolved to obtain a silver trifluoroacetate solution with the mass fraction of the silver trifluoroacetate of 15 wt%. The styrene-butadiene-styrene block copolymer flakes were then immersed in a silver trifluoroacetate solution for 30min, removed and dried. And completely immersing the dried sheet in 98% hydrazine hydrate solution for 30min, taking out, cleaning and drying to obtain the stretchable electromagnetic shielding elastic material of the silver nano particles/thermoplastic elastomer polymer. The cross-sectional structure is shown in fig. 6, the electromagnetic shielding effectiveness under different tensile strains is shown in fig. 7, the shielding effectiveness in the initial state is 80.2dB, and the shielding effectiveness is only 2.4dB when the tensile strain is 100%.
Comparative example 2
Adding carbon nanofiber and styrene-butadiene-styrene block copolymer into isophorone respectively to prepare a carbon nanofiber dispersion liquid with the mass fraction of 5wt% and a styrene-butadiene-styrene block copolymer solution with the mass fraction of 15wt%, carrying out ultrasonic treatment for 1h in an ultrasonic cell disruption instrument and magnetically stirring for 6h until the polymer is completely dissolved and the carbon nanofiber is uniformly dispersed. Mixing the carbon nanofiber dispersion liquid with a styrene-butadiene-styrene block copolymer solution to prepare a carbon nanofiber and styrene-butadiene-styrene block copolymer with the mass ratio of 3:17, and magnetically stirring the mixed solution for 6 hours until the carbon nanofibers are uniformly dispersed in the solution. Pouring the obtained mixed solution into a mould, and drying for 12 hours in a blowing drying box at 80 ℃ to obtain the carbon nanofiber/styrene-butadiene-styrene block copolymer sheet. The cross-sectional structure is shown in fig. 8, the electromagnetic shielding effectiveness under different tensile strains is shown in fig. 9, the shielding effectiveness in the initial state is 14.9dB, and the shielding effectiveness in the tensile strain is 100% is only 2.7dB.
Table 1 summary of examples and comparative examples.
As can be seen from Table 1, the stretchable electromagnetic shielding material prepared by the method of the present invention can effectively improve electromagnetic shielding performance under different stretching states. In particular, in example 4, the electromagnetic shielding performance of 30dB or more can be maintained even when the tensile strain reaches 100%.
Although the invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and the invention is therefore to be limited only by the terms of the appended claims.
Claims (10)
1. A stretchable electromagnetic shielding elastic material, characterized in that it comprises a thermoplastic elastomer polymer, a fibrous carbon filler and silver nanoparticles; the stretchable electromagnetic shielding elastic material is provided with a thermoplastic elastomer polymer substrate containing fibrous carbon fillers, and the surface and the inside of the substrate are provided with embedded silver nano particles; wherein the mass fraction of the thermoplastic elastomer polymer in the stretchable electromagnetic shielding elastic material is 40-60%, the mass fraction of the fibrous carbon filler in the stretchable electromagnetic shielding elastic material is 2-10%, and the mass fraction of the silver nano particles in the stretchable electromagnetic shielding elastic material is 30-58%;
the stretchable electromagnetic shielding elastic material is a layered material, and the thickness of the stretchable electromagnetic shielding elastic material is 200 mu m-10mm;
the stretchable electromagnetic shielding elastomeric material comprises silver nanoparticles in a thermoplastic elastomeric polymer in a depth range of 0-120 μm from the surface;
the preparation method of the stretchable electromagnetic shielding elastic material comprises the following steps:
(1) Preparing a thermoplastic elastomer polymer solution and a fibrous carbon filler dispersion: respectively dissolving a thermoplastic elastomer polymer and a fibrous carbon filler in an organic solvent, and uniformly mixing to obtain a thermoplastic elastomer polymer solution and a fibrous carbon filler dispersion;
(2) Preparing a fibrous carbon filler and thermoplastic elastomer polymer mixed solution: mixing the fibrous carbon filler dispersion liquid with the thermoplastic elastomer polymer solution until the fibrous carbon filler is uniformly dispersed in the mixed solution to obtain a fibrous carbon filler and thermoplastic elastomer polymer mixed solution;
(3) Pouring and drying: pouring the fibrous carbon filler/thermoplastic elastomer polymer solution obtained in the step (2) into a mold, and drying to obtain a fibrous carbon filler and thermoplastic elastomer polymer composite material;
(4) Preparing silver salt solution: mixing silver salt with an organic solvent to obtain silver salt solution;
(5) Adsorption of silver trifluoroacetate: immersing the fibrous carbon filler and thermoplastic elastomer polymer composite material obtained in the step (3) into the silver salt solution obtained in the step (4), taking out and drying to obtain the fibrous carbon filler and thermoplastic elastomer polymer composite material adsorbed with silver salt;
(6) And (3) reduction: immersing the fibrous carbon filler and thermoplastic elastomer polymer composite material with silver salt adsorbed on the surface obtained in the step (5) into a reducing agent solution for reduction, taking out, cleaning and drying to obtain the silver nanoparticle/fibrous carbon filler/thermoplastic elastomer polymer composite stretchable flexible electromagnetic shielding material.
2. The stretchable electromagnetic shielding elastomeric material of claim 1 wherein the thermoplastic elastomeric polymer is selected from the group consisting of styrenic elastomeric materials that are at least one of styrene-divinylbenzene-styrene block copolymers, styrene-butadiene-styrene block copolymers SBS, hydrogenated styrene-butadiene-styrene block copolymers SEBS, styrene-isoprene-styrene block copolymers SIS, hydrogenated styrene-isoprene copolymers, and modified or grafted elastomers thereof.
3. The stretchable electromagnetic shielding elastomeric material of claim 1 wherein the fibrous carbon filler is selected from the group consisting of carbon nanofibers, carbon nanotubes, and carbon fibers.
4. The stretchable electromagnetic shielding elastic material according to claim 1, wherein the thermoplastic elastomer polymer accounts for 40% -46% of the stretchable electromagnetic shielding elastic material in mass, the fibrous carbon filler accounts for 4% -8% of the stretchable electromagnetic shielding elastic material in mass, and the silver nanoparticle accounts for 50% -55% of the stretchable electromagnetic shielding elastic material in mass.
5. The stretchable electromagnetic shielding elastomeric material of claim 1, wherein the stretchable electromagnetic shielding elastomeric material comprises silver nanoparticles in the thermoplastic elastomeric polymer in a depth range of 0-100 μm from the surface.
6. A method for producing a stretchable electromagnetic shielding elastic material according to any one of claims 1 to 5, characterized in that the production step thereof comprises:
(1) Preparing a thermoplastic elastomer polymer solution and a fibrous carbon filler dispersion: respectively dissolving a thermoplastic elastomer polymer and a fibrous carbon filler in an organic solvent, and uniformly mixing to obtain a thermoplastic elastomer polymer solution and a fibrous carbon filler dispersion;
(2) Preparing a fibrous carbon filler and thermoplastic elastomer polymer mixed solution: mixing the fibrous carbon filler dispersion liquid with the thermoplastic elastomer polymer solution until the fibrous carbon filler is uniformly dispersed in the mixed solution to obtain a fibrous carbon filler and thermoplastic elastomer polymer mixed solution;
(3) Pouring and drying: pouring the fibrous carbon filler/thermoplastic elastomer polymer solution obtained in the step (2) into a mold, and drying to obtain a fibrous carbon filler and thermoplastic elastomer polymer composite material;
(4) Preparing silver salt solution: mixing silver salt with an organic solvent to obtain silver salt solution;
(5) Adsorption of silver trifluoroacetate: immersing the fibrous carbon filler and thermoplastic elastomer polymer composite material obtained in the step (3) into the silver salt solution obtained in the step (4), taking out and drying to obtain the fibrous carbon filler and thermoplastic elastomer polymer composite material adsorbed with silver salt;
(6) And (3) reduction: immersing the fibrous carbon filler and thermoplastic elastomer polymer composite material with silver salt adsorbed on the surface obtained in the step (5) into a reducing agent solution for reduction, taking out, cleaning and drying to obtain the silver nanoparticle/fibrous carbon filler/thermoplastic elastomer polymer composite stretchable flexible electromagnetic shielding material.
7. The method according to claim 6, wherein in the step (1), the fibrous carbon filler is mixed with the solvent at a mass ratio of 1: 19-3: 17, the mass ratio of the thermoplastic elastomer polymer to the solvent mixture is 1: 9-1: 5.
8. the method according to claim 6, wherein the silver salt in the step (4) is selected from silver trifluoroacetate, and the mass fraction of the silver salt in the silver salt solution in the step (4) is 5% -20%.
9. The method according to claim 6, wherein the reducing agent solvent in the step (6) is selected from hydrazine hydrate solutions having a concentration of 50%.
10. Use of the stretchable electromagnetic shielding elastic material according to any one of claims 1 to 5 as an electromagnetic shielding material in the preparation of an electronic product.
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