CN112793269B - Electromagnetic shielding composite material with multilayer structure and preparation method and application thereof - Google Patents

Electromagnetic shielding composite material with multilayer structure and preparation method and application thereof Download PDF

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Publication number
CN112793269B
CN112793269B CN202011605983.3A CN202011605983A CN112793269B CN 112793269 B CN112793269 B CN 112793269B CN 202011605983 A CN202011605983 A CN 202011605983A CN 112793269 B CN112793269 B CN 112793269B
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layer
composite material
filler
shielding composite
resin
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CN112793269A (en
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冉祥海
王春博
付超
聂伟
钱景
高一星
楚慧颖
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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Abstract

The invention provides an electromagnetic shielding composite material, which comprises an absorption layer and a reflection layer compounded on the absorption layer; the absorbent layer includes a modified resin layer; the reflective layer includes a metal nanowire film layer. The electromagnetic shielding composite material with the specific structure and the composition is obtained by adopting the specific layer material and combining the laminated structure of the absorption layer and the reflection layer. The multilayer-structure electromagnetic shielding composite material prepared by utilizing the laminated structure of the absorption layer and the reflection layer has the advantages of high electromagnetic shielding efficiency, low electromagnetic wave reflection, excellent mechanical property and the like, and can be applied to the fields of emerging 5G communication and aerospace instead of the traditional electromagnetic shielding composite material.

Description

Electromagnetic shielding composite material with multilayer structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electromagnetic shielding materials, relates to an electromagnetic shielding composite material, and a preparation method and application thereof, and particularly relates to an electromagnetic shielding composite material with a multilayer structure, and a preparation method and application thereof.
Background
The development of electronic information technology brings great convenience to people and simultaneously generates a great deal of electromagnetic pollution. A large amount of electromagnetic pollution influences the normal operation of instruments and equipment, and especially the requirements on the anti-interference capability of signals in the emerging 5G communication field and the aerospace field are stricter. Accordingly, various electromagnetic shielding composite materials have been developed.
The traditional electromagnetic shielding composite material mostly adopts a blending process to mix polymer resin and filler, and the shielding effectiveness depends on the continuity degree of a conductive network. Because the filler is easy to agglomerate in the matrix, a large amount of conductive filler (such as metal powder, carbon nano tubes, carbon fibers, graphene and the like) is usually required to be added to obtain good conductive performance. Meanwhile, the impedance mismatch between the composite material and air can be caused by the addition of a large amount of filler in the resin matrix, so that a large amount of electromagnetic reflection is caused, and secondary electromagnetic wave pollution is caused. Meanwhile, the mechanical property of the composite material is greatly reduced due to the addition of a large amount of filler in the resin matrix, and the actual application cannot be met.
Therefore, how to find a suitable electromagnetic shielding composite material to solve the above problems of the existing electromagnetic shielding composite materials has become one of the problems to be solved by the prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an electromagnetic shielding composite material, a method for preparing the same, and an application of the same, and in particular, to an electromagnetic shielding composite material with a multilayer structure.
The invention provides an electromagnetic shielding composite material, which comprises an absorption layer and a reflection layer compounded on the absorption layer;
the absorbent layer includes a modified resin layer;
the reflective layer includes a metal nanowire film layer.
Preferably, the thickness of the absorption layer is 50 to 200 μm;
the thickness of the reflecting layer is 1-5 mu m;
the metal comprises one or more of gold, silver and copper;
the electromagnetic shielding composite material has a multilayer structure with 4 layers or more.
Preferably, the diameter of the metal nanowire is 50-200 nm;
the length of the metal nanowire is 10-50 μm;
in the metal nanowire film layer, the metal nanowires have a shape structure which is stacked in a staggered mode;
the resin matrix of the modified resin comprises one or more of polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene fluoride resin, polyurethane resin and polyphenyl ether resin;
the modified resin includes a resin and a modified filler.
Preferably, the mass ratio of the resin to the modified filler is (70-90): (10-30);
the modified filler is prepared from a filler A and a filler B;
the filler A comprises one or more of nickel powder, titanium carbide, expanded graphite, flake graphite and graphene nanosheets;
the filler B comprises graphene oxide and/or acidified carbon nanotubes;
the mass ratio of the filler A to the filler B is 1: (0.5 to 1);
the electromagnetic shielding composite material is provided with an absorption layer and a reflection layer which are alternately laminated;
the number of the absorption layer/reflection layer layers which are alternately stacked is not less than 2.
The invention provides a preparation method of an electromagnetic shielding composite material, which comprises the following steps:
1) Mixing the filler A with a solvent, adding the filler B, continuously mixing, adding ferric chloride, alkali and hydrazine hydrate, mixing again, and reacting to obtain a modified filler;
2) Extruding and granulating the modified filler and the resin obtained in the step to obtain modified resin;
3) Carrying out hot pressing on the modified resin obtained in the step to obtain a modified resin layer;
4) And compounding the metal nanowire dispersion liquid subjected to plasma treatment on the modified resin layer to obtain the electromagnetic shielding composite material.
Preferably, the filler A comprises one or more of nickel powder, titanium carbide, expanded graphite, flake graphite and graphene nanosheets;
the solvent comprises one or more of methanol, ethanol and glycol;
the mixing time is 1-3 h;
the filler B comprises graphene oxide and/or acidified carbon nanotubes;
the mass ratio of the filler A to the filler B is 1: (0.5-1);
the mass ratio of the filler A to the solvent is 1: (100-300).
Preferably, the mixing and the continuing mixing respectively comprise ultrasonic dispersion;
the time for continuously mixing is 1-3 h;
the alkali comprises potassium hydroxide and sodium hydroxide;
the mass ratio of the ferric chloride to the filler B is (10-30): 1;
the mass ratio of the alkali to the ferric chloride is (3-5): 1;
the mass ratio of the hydrazine hydrate to the ferric chloride is 1: (8-10).
Preferably, the time for mixing again is 2 to 4 hours;
the reaction temperature is 160-200 ℃;
the reaction time is 8-16 h;
the temperature of the extrusion granulation is 160-300 ℃;
the rotating speed of the extrusion granulation is 30-120 rpm.
Preferably, the concentration of the metal nanowire dispersion liquid is 2-10 mg/ml;
the solvent of the metal nanowire dispersion liquid comprises ethanol, methanol, a polyvinyl alcohol aqueous solution with the mass fraction of 5%, a polyvinyl alcohol aqueous solution with the mass fraction of 7% or a polyvinyl alcohol aqueous solution with the mass fraction of 10%;
the plasma treatment time is 30-60 s;
the compound mode comprises spraying;
and drying after compounding.
The invention also provides an application of the electromagnetic shielding composite material in any one of the technical schemes or the electromagnetic shielding composite material prepared by the preparation method in any one of the technical schemes in the 5G communication field or the aerospace field.
The invention provides an electromagnetic shielding composite material, which comprises an absorption layer and a reflection layer compounded on the absorption layer; the absorbent layer includes a modified resin layer; the reflective layer includes a metal nanowire film layer. Compared with the prior art, the electromagnetic shielding composite material with a specific structure and composition is obtained by adopting a specific layer material and combining an absorption layer-reflection layer laminated structure. The electromagnetic shielding composite material provided by the invention can realize high electromagnetic shielding efficiency and low electromagnetic reflection, has excellent mechanical properties, and effectively solves the problem that the existing conductive composite material prepared by a direct blending method can achieve ideal shielding performance only by adding a large amount of filler into a resin matrix, and the mechanical properties of the whole composite material are reduced by adding a large amount of filler, so that the actual requirements are difficult to meet; a large amount of electromagnetic wave reflection easily causes secondary pollution and the like.
The multilayer-structure electromagnetic shielding composite material prepared by utilizing the alternate laminated structure of the absorption layer and the reflection layer has the advantages of high electromagnetic shielding efficiency, low electromagnetic wave reflection, excellent mechanical property and the like, and can be applied to the fields of emerging 5G communication and aerospace instead of the traditional electromagnetic shielding composite material.
Experimental results show that the highest shielding effectiveness of the electromagnetic shielding composite material with the multilayer structure is 72.4dB at the frequency of 9.5GHz, the electromagnetic shielding composite material is obviously superior to 52.9dB of a sample prepared by a blending method at the same content, the absorption efficiency is up to 85% at most, and secondary pollution caused by reflection of a large amount of electromagnetic waves is greatly reduced. Meanwhile, the prepared sample has excellent mechanical properties, and meets the mechanical property requirements of the electromagnetic shielding material in the application of the emerging 5G communication field and the aerospace field.
Drawings
FIG. 1 is a schematic diagram of a process for preparing an electromagnetic shielding composite material with a multilayer structure according to the present invention;
FIG. 2 shows the shielding effectiveness of the electromagnetic shielding composite material with a multilayer structure provided by the present invention under the condition of 1-12 GHz.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a conventional purity used in the field of analytical purification or electromagnetic shielding composite materials.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides an electromagnetic shielding composite material, which comprises an absorption layer and a reflection layer compounded on the absorption layer;
the absorbent layer includes a modified resin layer;
the reflective layer includes a metal nanowire film layer.
In the present invention, the thickness of the reflective layer is preferably 1 to 5 μm, more preferably 1.5 to 4.5 μm, more preferably 2 to 4 μm, and more preferably 2.5 to 3.5 μm.
In the present invention, the metal preferably includes one or more of gold, silver and copper, and more preferably gold, silver or copper.
In the present invention, the diameter of the metal nanowire is preferably 50 to 200nm, more preferably 80 to 170nm, and still more preferably 110 to 140nm.
In the present invention, the length of the metal nanowire is preferably 10 to 50 μm, more preferably 15 to 45 μm, more preferably 20 to 40 μm, and more preferably 25 to 35 μm.
In the present invention, in the metal nanowire film layer, the metal nanowires preferably have a staggered and stacked morphology structure.
In the present invention, the thickness of the absorption layer is preferably 50 to 200. Mu.m, more preferably 80 to 150. Mu.m, and still more preferably 110 to 130. Mu.m.
In the present invention, the resin matrix of the modified resin preferably includes one or more of a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, a polyvinylidene fluoride resin, a polyurethane resin, and a polyphenylene ether resin, and more preferably a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, a polyvinylidene fluoride resin, a polyurethane resin, or a polyphenylene ether resin.
In the present invention, the modified resin preferably includes a resin and a modified filler.
In the present invention, the mass ratio of the resin to the modified filler is preferably (70 to 90): (10 to 30), more preferably (74 to 86): (10 to 30), more preferably (78 to 82): (10 to 30), more preferably (70 to 90): (14 to 26), more preferably (70 to 90): (18 to 22). In the present invention, the mass ratio is preferably in terms of the mass ratio of the raw materials, that is, the modified resin in the present invention is preferably obtained by preparing the resin and the modified filler.
In the present invention, the modified filler is preferably prepared from filler a and filler B.
In the present invention, the filler a preferably includes one or more of nickel powder, titanium carbide, expanded graphite, flake graphite, and graphene nanoplatelets, and more preferably includes nickel powder, titanium carbide, expanded graphite, flake graphite, or graphene nanoplatelets.
In the present invention, the filler B preferably includes graphene oxide and/or acidified carbon nanotubes, and more preferably graphene oxide or acidified carbon nanotubes.
In the present invention, the mass ratio of the filler a to the filler B is preferably 1: (0.5 to 1), more preferably 1: (0.6 to 0.9), more preferably 1: (0.7-0.8).
In the present invention, the electromagnetic shielding composite material preferably has a multilayer structure of 4 or more layers, more preferably 8 or more layers, and still more preferably 10 or more layers.
In the present invention, the electromagnetic shielding composite preferably has an absorption layer and a reflection layer which are alternately laminated.
In the present invention, the number of alternately stacked absorption layers/reflection layers is preferably 2 or more, more preferably 3 or more, and still more preferably 5 or more.
In the present invention, the number of alternately stacked absorption layers/reflection layers is preferably 2 or more, that is, 2 or more layers. In the present invention, the absorption layer and the reflection layer are 1 stack of alternating layers, and the number of the stack of alternating layers is preferably 2 or more.
The invention provides a preparation method of an electromagnetic shielding composite material, which comprises the following steps:
1) Mixing the filler A with a solvent, adding the filler B, continuously mixing, adding ferric chloride, alkali and hydrazine hydrate, mixing again, and reacting to obtain a modified filler;
2) Extruding and granulating the modified filler and the resin obtained in the step to obtain modified resin;
3) Carrying out hot pressing on the modified resin obtained in the step to obtain a modified resin layer;
4) And compounding the metal nanowire dispersion liquid subjected to plasma treatment on the modified resin layer to obtain the electromagnetic shielding composite material.
The selection and composition of the raw materials required in the preparation process, and the corresponding preferred principle of the present invention can correspond to the selection and composition of the raw materials corresponding to the electromagnetic shielding composite material, and the corresponding preferred principle of the present invention, which are not described in detail herein.
Firstly, mixing a filler A with a solvent, then adding a filler B, continuously mixing, then adding ferric chloride, alkali and hydrazine hydrate, mixing again, and reacting to obtain the modified filler.
In the present invention, the filler a preferably includes one or more of nickel powder, titanium carbide, expanded graphite, flake graphite, and graphene nanoplatelets, and more preferably includes nickel powder, titanium carbide, expanded graphite, flake graphite, or graphene nanoplatelets.
In the present invention, the solvent preferably includes one or more of methanol, ethanol and ethylene glycol, more preferably methanol, ethanol or ethylene glycol.
In the present invention, the mixing time is preferably 1 to 3 hours, more preferably 1.4 to 2.6 hours, and still more preferably 1.8 to 2.2 hours.
In the present invention, the filler B preferably includes graphene oxide and/or acidified carbon nanotubes, and more preferably graphene oxide or acidified carbon nanotubes.
In the present invention, the mass ratio of the filler a to the filler B is preferably 1: (0.5 to 1), more preferably 1: (0.6 to 0.9), more preferably 1: (0.7-0.8).
In the present invention, the mass ratio of the filler a to the solvent is preferably 1: (100 to 300), more preferably 1: (140 to 260), more preferably 1: (180-220).
In the present invention, the mixing and the manner of continuing the mixing each preferably include ultrasonic dispersion.
In the present invention, the time for continuing the mixing is preferably 1 to 3 hours, more preferably 1.4 to 2.6 hours, and still more preferably 1.8 to 2.2 hours.
In the present invention, the alkali preferably includes potassium hydroxide and sodium hydroxide.
In the present invention, the mass ratio of the iron chloride to the filler B is preferably (10 to 30): 1, more preferably (14 to 26): 1, more preferably (18 to 22): 1.
in the present invention, the mass ratio of the alkali to the ferric chloride is preferably (3 to 5): 1, more preferably (3.4 to 4.6): 1, more preferably (3.8 to 4.2): 1.
in the present invention, the mass ratio of hydrazine hydrate to ferric chloride is preferably 1: (8 to 10), more preferably 1: (8.4 to 9.6), more preferably 1: (8.8-9.2).
In the present invention, the time for the remixing is preferably 2 to 4 hours, more preferably 2.4 to 3.6 hours, and still more preferably 2.8 to 3.2 hours.
In the present invention, the temperature of the reaction is preferably 160 to 200 ℃, more preferably 165 to 195 ℃, more preferably 170 to 190 ℃, more preferably 175 to 185 ℃.
In the present invention, the reaction time is preferably 8 to 16 hours, more preferably 9 to 15 hours, more preferably 10 to 14 hours, and more preferably 11 to 13 hours.
The modified filler and the resin obtained in the steps are extruded and granulated to obtain the modified resin.
In the present invention, the temperature for extrusion granulation is preferably 160 to 300 ℃, more preferably 180 to 280 ℃, more preferably 200 to 260 ℃, and more preferably 220 to 240 ℃.
In the present invention, the rotation speed of the extrusion granulation is preferably 30 to 120rpm, more preferably 50 to 100rpm, and still more preferably 70 to 80rpm.
The invention then carries out hot pressing on the modified resin obtained in the step to obtain a modified resin layer with the thickness of 50-200 mu m.
Finally, compounding the metal nanowire dispersion liquid subjected to plasma treatment on a modified resin layer to obtain the electromagnetic shielding composite material.
In the present invention, the concentration of the metal nanowire dispersion is preferably 2 to 10mg/ml, more preferably 3 to 9mg/ml, more preferably 4 to 8mg/ml, and more preferably 5 to 7mg/ml.
In the present invention, the solvent of the metal nanowire dispersion preferably includes ethanol, methanol, a 5% by mass aqueous solution of polyvinyl alcohol, a 7% by mass aqueous solution of polyvinyl alcohol, or a 10% by mass aqueous solution of polyvinyl alcohol.
In the present invention, the time for the plasma treatment is preferably 30 to 60 seconds, more preferably 35 to 55 seconds, and still more preferably 40 to 50 seconds.
In the present invention, the compounding means preferably includes spraying.
In the present invention, the compounding preferably includes a drying step.
In the present invention, when the number of alternately stacked layers is preferably 2 or more, step 5),
5) And (3) laminating the electromagnetic shielding composite materials obtained in the above steps, and carrying out hot pressing again to obtain the electromagnetic shielding composite material with a multilayer structure.
The parameters of said re-hot pressing are not particularly restricted by the present invention, as is conventional for such operations, well known to those skilled in the art.
The invention is a complete and detailed integral technical scheme, and the preparation method of the electromagnetic shielding composite material can specifically comprise the following steps:
1) Preparing a modified filler:
firstly, adding a certain mass of filler A into a solvent for ultrasonic dispersion for 1-3 h, adding a filler B, continuing ultrasonic dispersion for 1-3 h, respectively adding ferric chloride, alkali and hydrazine hydrate into the dispersion liquid, stirring for 2-4 h, transferring the mixed liquid into an autoclave, and treating for 8-16 h at 160-200 ℃. Finally, cooling to room temperature, filtering, washing, and drying at 80-120 ℃ to obtain the final modified filler.
2) Preparing modified resin:
weighing a certain mass of resin and modified filler, and extruding and granulating at a certain temperature and a certain rotating speed by an extruder to obtain the modified resin.
3) Preparation of an absorption layer:
the obtained modified resin is hot-pressed at a certain temperature and pressure to obtain a film with a certain thickness, namely an absorption layer.
4) Preparation of an absorption/reflection layer:
dispersing metal nano wire in solvent at concentration of 2-10 mg/ml, treating the obtained film with plasma for 30-60 s, spraying the metal nano wire dispersion liquid on the surface of the film, drying to obtain the absorption/reflection layer
5) Preparing an electromagnetic shielding composite material with a multilayer structure:
and laminating the absorption/reflection layers, and then carrying out hot pressing at certain temperature and pressure to obtain the electromagnetic shielding composite material with the multilayer structure.
Referring to fig. 1, fig. 1 is a schematic diagram of a technical route for preparing an electromagnetic shielding composite material with a multilayer structure according to the present invention.
The invention also provides an application of the electromagnetic shielding composite material in any one of the technical schemes or the electromagnetic shielding composite material prepared by the preparation method in any one of the technical schemes in the 5G communication field or the aerospace field.
The invention provides an electromagnetic shielding composite material with a multilayer structure, and a preparation method and application thereof. The electromagnetic shielding composite material with the specific structure and the specific composition is obtained by adopting the specific layer material and combining the alternate laminated structure of the absorption layer and the reflection layer. The composite material with the structure realizes high electromagnetic shielding efficiency, low electromagnetic reflection and excellent mechanical property. The alternate laminated structure design of the absorption layer and the reflection layer of the composite material provided by the invention endows the material with low electromagnetic wave reflection, and avoids harm caused by electromagnetic wave secondary pollution; meanwhile, the composite material prepared by the invention has excellent mechanical property, and can meet the requirements on the mechanical property of the composite material in the practical application process while meeting the electromagnetic shielding property. The invention effectively solves the problems that the prior conductive composite material prepared by a direct blending method can achieve ideal shielding performance only by adding a large amount of filler into a resin matrix, the mechanical performance of the whole composite material is reduced by adding a large amount of filler, the actual requirement is difficult to meet, secondary pollution is easily caused by the reflection of a large amount of electromagnetic waves, and the like.
The multilayer-structure electromagnetic shielding composite material prepared by utilizing the alternate laminated structure of the absorption layer and the reflection layer has the advantages of high electromagnetic shielding efficiency, low electromagnetic wave reflection, excellent mechanical property and the like, and can be applied to the emerging 5G communication field and the aerospace field instead of the traditional electromagnetic shielding composite material.
Experimental results show that the highest shielding effectiveness of the electromagnetic shielding composite material with the multilayer structure is 72.4dB at the frequency of 9.5GHz, the electromagnetic shielding composite material is obviously superior to 52.9dB of a sample prepared by a blending method at the same content, the absorption efficiency is up to 85% at most, and secondary pollution caused by reflection of a large amount of electromagnetic waves is greatly reduced. Meanwhile, the prepared sample has excellent mechanical properties, and meets the mechanical property requirements of the electromagnetic shielding material in the application of the emerging 5G communication field and the aerospace field.
For further illustration of the present invention, the following will describe an electromagnetic shielding composite material and its preparation method and application in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
1) Preparing modified filler:
firstly, 1g of graphene nanosheet is added into methanol for ultrasonic dispersion for 3 hours, then 1g of graphene oxide is added, then 3 hours and 30g of ferric chloride, 150g of sodium hydroxide and 3.75g of hydrazine hydrate are added into the dispersion liquid respectively for stirring for 4 hours under ultrasonic action, the mixed liquid is transferred into an autoclave, and the mixed liquid is treated for 16 hours at 200 ℃. And finally, cooling to room temperature, filtering, washing, and drying at 120 ℃ to obtain the final modified filler.
2) Preparing modified resin:
7g of polyethylene resin and 3g of modified filler are weighed and extruded and granulated by an extruder at the temperature of 160-220 ℃ and the rotating speed of 30rpm to obtain the modified resin.
3) Preparation of an absorption layer:
the obtained modified resin was hot-pressed at a temperature of 160 ℃ and a pressure of 1MPa to obtain a 200um film, i.e., an absorbent layer.
4) Preparation of an absorption/reflection layer:
dispersing silver nanowire (length: 50um; diameter: 50 nm) in ethanol at concentration of 10mg/ml, treating the obtained film with plasma for 60s, spraying silver nanowire dispersion on the surface of the film, drying, and spraying to a thickness of 5um to obtain an absorption/reflection layer
5) Preparing the electromagnetic shielding composite material with the multilayer structure:
and (3) laminating 5 absorption/reflection layers, and then carrying out hot pressing at the temperature of 160 ℃ and the pressure of 1MPa to obtain the electromagnetic shielding composite material with the multilayer structure. The shielding effectiveness is 59.5-75.6dB under the condition of 1-12 GHz, and the absorption efficiency is 85% under the condition of 9.5 GHz.
The performance of the electromagnetic shielding composite material with the multilayer structure prepared in the embodiment 1 of the invention is detected.
Referring to table 1, table 1 shows the electromagnetic shielding effectiveness (9.5 GHz) and mechanical properties of the electromagnetic shielding composite material with the multilayer structure provided in example 1 of the present invention and the composite material prepared by the blending method under the same filler content.
TABLE 1
Figure BDA0002873444740000101
Figure BDA0002873444740000111
Wherein SET: the total electromagnetic shielding effectiveness; SEA: absorption efficiency of electromagnetic waves; SER: reflection efficiency of electromagnetic waves; t iss: tensile strength; eb: elongation at break.
Table 1 shows the test results of the 5 absorption/reflection layers after lamination and hot pressing, the matrix resin is polyethylene, the addition amount of the modified filler is 30%,10mg/ml metal nanowires are sprayed on the surface of the modified resin, and the 5 absorption/reflection layers are laminated and hot pressed.
As can be seen from table 1, the shielding effectiveness of the electromagnetic shielding composite material with a multilayer structure prepared in example 1 of the present invention is 72.4dB at a frequency of 9.5GHz, which is significantly better than the shielding effectiveness of 52.9dB of a sample prepared by a blending method at the same content, wherein the absorption shielding effectiveness is 61.5dB, the reflection shielding effectiveness is 10.9dB, and the absorption efficiency is as high as 85%. Meanwhile, the prepared sample has excellent mechanical properties, the tensile strength is 18.4MPa, and the elongation at break is 280%.
Referring to fig. 2, fig. 2 shows the shielding effectiveness of the electromagnetic shielding composite material with a multilayer structure provided by the invention under the condition of 1 to 12 GHz.
As can be seen from FIG. 2, the electromagnetic shielding composite material with a multilayer structure of the present invention shows excellent electromagnetic shielding performance under the condition of 1-12 GHz.
Example 2
1) Preparing a modified filler:
firstly, 1g of flake graphite is added into ethanol for ultrasonic dispersion for 1h, then 0.5g of acidified carbon nano tube is added, ultrasonic treatment is continued for 1h,5g of ferric chloride, 15g of potassium hydroxide and 0.625g of hydrazine hydrate are respectively added into the dispersion liquid for stirring for 2h, the mixed liquid is transferred into an autoclave, and the treatment is carried out for 8h at 160 ℃. And finally, cooling to room temperature, filtering, washing, and drying at 80 ℃ to obtain the final modified filler.
2) Preparing modified resin:
9g of polypropylene and 1g of modified filler are weighed and extruded and granulated by an extruder at the temperature of 170-230 ℃ and the rotating speed of 120rpm to obtain the modified resin.
3) Preparation of an absorption layer:
the obtained modified resin was hot-pressed at a temperature of 170 ℃ and a pressure of 0.5MPa to obtain a film having a thickness of 50um, i.e., an absorption layer.
4) Preparation of an absorption/reflection layer:
dispersing gold nanowires (length: 10um; diameter: 200 nm) in methanol solvent at a concentration of 2mg/ml, treating the obtained film with plasma for 30s, then spraying gold nanowire dispersion on the surface of the film, drying, and spraying to a thickness of 1um to obtain an absorption/reflection layer
5) Preparing an electromagnetic shielding composite material with a multilayer structure:
2 layers of absorption/reflection layers are laminated and then hot-pressed at the temperature of 170 ℃ and the pressure of 0.5MPa to obtain the electromagnetic shielding composite material with the multilayer structure. The shielding effectiveness is 21.6-25.3dB under the condition of 1-12 GHz, and the absorption efficiency is 78% under the condition of 9.5 GHz.
Example 3
1) Preparing modified filler:
firstly, 1g of expanded graphite is added into ethylene glycol for ultrasonic dispersion for 2 hours, then 0.75g of graphene oxide is added, ultrasonic treatment is continued for 2hours, 15g of ferric chloride, 60g of sodium hydroxide and 1.67g of hydrazine hydrate are respectively added into the dispersion liquid for stirring for 3 hours, the mixed liquid is transferred into an autoclave, and the treatment is carried out for 12 hours at 180 ℃. And finally, cooling to room temperature, filtering, washing, and drying at 100 ℃ to obtain the final modified filler.
2) Preparing modified resin:
weighing 8g of polyvinyl chloride resin and 2g of modified filler, and extruding and granulating at the temperature of 160-190 ℃ and the rotating speed of 80rpm by using an extruder to obtain the modified resin.
3) Preparation of an absorption layer:
the obtained modified resin was hot-pressed at a temperature of 160 ℃ and a pressure of 0.75MPa to obtain a film having a thickness of 100um, i.e., an absorbent layer.
4) Preparation of an absorption/reflection layer:
dispersing copper nanowires (length: 30um; diameter: 150 nm) in 5% polyvinyl alcohol aqueous solution at a concentration of 6mg/ml, treating the obtained film with plasma for 45s, then spraying the copper nanowire dispersion on the surface of the film, drying, and spraying to a thickness of 3um to obtain an absorption/reflection layer
5) Preparing an electromagnetic shielding composite material with a multilayer structure:
and laminating 3 absorbing/reflecting layers, and then carrying out hot pressing at the temperature of 160 ℃ and the pressure of 0.75MPa to obtain the electromagnetic shielding composite material with the multilayer structure. The shielding effectiveness is 38.9-45.3dB under the condition of 1-12 GHz, and the absorption efficiency is 81% under the condition of 9.5 GHz.
Example 4
1) Preparing modified filler:
firstly, 1g of titanium carbide is added into methanol for 3 hours of ultrasonic dispersion, 1g of graphene oxide is added, then, 3 hours and 30g of ferric chloride, 150g of sodium hydroxide and 3.75g of hydrazine hydrate are added into the dispersion liquid respectively for stirring for 4 hours, and the mixed liquid is transferred into an autoclave for treatment for 16 hours at 200 ℃. And finally, cooling to room temperature, filtering, washing, and drying at 120 ℃ to obtain the final modified filler.
2) Preparing modified resin:
weighing 7g of polyvinylidene fluoride resin and 3g of modified filler, and carrying out extrusion granulation by an extruder at the temperature of 190-230 ℃ and the rotating speed of 30rpm to obtain the modified resin.
3) Preparation of an absorption layer:
the obtained modified resin was hot-pressed at a temperature of 190 ℃ and a pressure of 1MPa to obtain a 200um film, i.e., an absorbent layer.
4) Preparation of an absorption/reflection layer:
dispersing silver nanowires (length: 10um; diameter: 100 nm) in 7% polyvinyl alcohol aqueous solution at a concentration of 10mg/ml, treating the obtained film with plasma for 60s, spraying silver nanowire dispersion on the surface of the film, drying, and spraying to a thickness of 5um to obtain an absorption/reflection layer
5) Preparing the electromagnetic shielding composite material with the multilayer structure:
and (3) laminating 5 absorbing/reflecting layers, and then carrying out hot pressing at the temperature of 190 ℃ and under the pressure of 1MPa to obtain the electromagnetic shielding composite material with the multilayer structure. The shielding effectiveness is 56.3-72.8dB under the condition of 1-12 GHz, and the absorption efficiency is 82% under the condition of 9.5 GHz.
Example 5
1) Preparing modified filler:
firstly, 1g of nickel powder is added into methanol for ultrasonic dispersion for 3 hours, then 1g of graphene oxide is added, ultrasonic treatment is continued for 3 hours, 30g of ferric chloride, 150g of sodium hydroxide and 3.75g of hydrazine hydrate are respectively added into the dispersion liquid for stirring for 4 hours, the mixed liquid is transferred into an autoclave, and the treatment is carried out for 16 hours at 200 ℃. And finally, cooling to room temperature, filtering, washing, and drying at 120 ℃ to obtain the final modified filler.
2) Preparing modified resin:
weighing 7g of polyurethane resin and 3g of modified filler, and extruding and granulating at the temperature of 170-210 ℃ and the rotating speed of 30rpm by using an extruder to obtain the modified resin.
3) Preparation of an absorption layer:
the obtained modified resin was hot-pressed at a temperature of 170 ℃ and a pressure of 1MPa to obtain a 200um film, i.e., an absorbent layer.
4) Preparation of an absorption/reflection layer:
dispersing silver nanowires (length: 50um; diameter: 50 nm) in 10mg/ml concentration in 10% polyvinyl alcohol aqueous solution, treating the obtained film with plasma for 60s, then spraying silver nanowire dispersion on the surface of the film, drying, and spraying to a thickness of 5um to obtain an absorption/reflection layer
5) Preparing an electromagnetic shielding composite material with a multilayer structure:
and (3) laminating 5 absorption/reflection layers, and then carrying out hot pressing at the temperature of 170 ℃ and the pressure of 1MPa to obtain the electromagnetic shielding composite material with the multilayer structure. The shielding effectiveness is 57.9-75.2dB under the condition of 1-12 GHz, and the absorption efficiency is 84% under the condition of 9.5 GHz.
Example 6
1) Preparing modified filler:
firstly, 1g of nickel powder is added into methanol for ultrasonic dispersion for 3 hours, then 1g of graphene oxide is added, ultrasonic treatment is continued for 3 hours, 30g of ferric chloride, 150g of sodium hydroxide and 3.75g of hydrazine hydrate are respectively added into the dispersion liquid for stirring for 4 hours, the mixed liquid is transferred into an autoclave, and the treatment is carried out for 16 hours at 200 ℃. And finally, cooling to room temperature, filtering, washing, and drying at 120 ℃ to obtain the final modified filler.
2) Preparing modified resin:
7g of polyphenylene ether resin and 3g of modified filler were weighed and subjected to extrusion granulation at a temperature of 260 to 300 ℃ and a rotation speed of 30rpm by an extruder to obtain a modified resin.
3) Preparation of an absorption layer:
the obtained modified resin was hot-pressed at a temperature of 260 ℃ and a pressure of 1MPa to obtain a 200um film, i.e., an absorbent layer.
4) Preparation of an absorption/reflection layer:
dispersing silver nanowires (length: 50um, diameter: 50 nm) in 10mg/ml concentration in 10% polyvinyl alcohol aqueous solution, treating the obtained film with plasma for 60s, then spraying silver nanowire dispersion liquid on the surface of the film, drying, and spraying to a thickness of 5um to obtain an absorption/reflection layer
5) Preparing an electromagnetic shielding composite material with a multilayer structure:
and (3) laminating 5 absorption/reflection layers, and then carrying out hot pressing at the temperature of 260 ℃ and under the pressure of 1MPa to obtain the electromagnetic shielding composite material with the multilayer structure. The shielding effectiveness is 56.5-73.7dB under the condition of 1-12 GHz, and the absorption efficiency is 83% under the condition of 9.5 GHz.
While the present invention has been described in detail with respect to a multi-layered electromagnetic shielding composite material, its preparation and application, and it is intended that the principles and embodiments of the present invention be illustrated herein using specific examples, the foregoing description of the embodiments is merely provided to facilitate the understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (9)

1. An electromagnetic shielding composite material is characterized by comprising an absorption layer and a reflection layer compounded on the absorption layer;
the absorbent layer includes a modified resin layer;
the reflective layer comprises a metal nanowire film layer;
the electromagnetic shielding composite material is provided with an absorption layer and a reflection layer which are alternately laminated;
the number of the absorption layer/reflection layer which are alternately laminated is more than or equal to 2;
the preparation method of the electromagnetic shielding composite material comprises the following steps:
1) Mixing the filler A with a solvent, adding the filler B, continuously mixing, adding ferric chloride, alkali and hydrazine hydrate, mixing again, and reacting to obtain a modified filler;
2) Extruding and granulating the modified filler and the resin obtained in the step to obtain modified resin;
3) Carrying out hot pressing on the modified resin obtained in the step to obtain a modified resin layer;
4) Compounding the metal nanowire dispersion liquid subjected to plasma treatment on the modified resin layer to obtain the electromagnetic shielding composite material;
the filler A comprises one or more of nickel powder, titanium carbide, expanded graphite, flake graphite and graphene nanosheets;
the filler B comprises graphene oxide and/or acidified carbon nanotubes.
2. The electromagnetically shielding composite of claim 1 wherein the thickness of said absorbing layer is 50-200 μm;
the thickness of the reflecting layer is 1-5 mu m;
the metal comprises one or more of gold, silver and copper.
3. The electromagnetically shielding composite material as claimed in claim 1, wherein the diameter of said metal nanowire is 50 to 200nm;
the length of the metal nanowire is 10-50 μm;
in the metal nanowire film layer, the metal nanowires have a shape structure which is stacked in a staggered mode;
the resin matrix of the modified resin comprises one or more of polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene fluoride resin, polyurethane resin and polyphenyl ether resin.
4. The electromagnetically shielding composite material as claimed in claim 1, 2 or 3, wherein the mass ratio of the resin to the modified filler is (70-90): (10-30);
the mass ratio of the filler A to the filler B is 1: 0.5-1.
5. The electromagnetically shielding composite as claimed in claim 4,
the solvent comprises one or more of methanol, ethanol and glycol;
the mixing time is 1-3 h;
the mass ratio of the filler A to the solvent is 1: 100-300.
6. The electromagnetically shielding composite of claim 4 wherein said means for mixing and continuing to mix each comprise ultrasonic dispersion;
the time for continuously mixing is 1-3 h;
the alkali comprises potassium hydroxide and sodium hydroxide;
the mass ratio of the ferric chloride to the filler B is (10-30) to 1;
the mass ratio of the alkali to the ferric chloride is (3-5) to 1;
the mass ratio of the hydrazine hydrate to the ferric chloride is 1: 8-10.
7. The electromagnetically shielding composite of claim 4 wherein the remixing time is between 2 and 4 hours;
the reaction temperature is 160-200 ℃;
the reaction time is 8-16 h;
the temperature of the extrusion granulation is 160-300 ℃;
the rotating speed of the extrusion granulation is 30-120 rpm.
8. The electromagnetic shielding composite material as claimed in claim 4, wherein the concentration of the metal nanowire dispersion is 2 to 10mg/ml;
the solvent of the metal nanowire dispersion liquid comprises ethanol, methanol, a polyvinyl alcohol aqueous solution with the mass fraction of 5%, a polyvinyl alcohol aqueous solution with the mass fraction of 7% or a polyvinyl alcohol aqueous solution with the mass fraction of 10%;
the plasma treatment time is 30-60 s;
the compound mode comprises spraying;
and a drying step is also included after the compounding.
9. Use of the electromagnetically shielding composite material as claimed in any one of claims 1 to 8 in the field of 5G communications or aerospace.
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