CN112261859A - Novel electromagnetic shielding material and preparation method thereof - Google Patents
Novel electromagnetic shielding material and preparation method thereof Download PDFInfo
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- CN112261859A CN112261859A CN202011124548.9A CN202011124548A CN112261859A CN 112261859 A CN112261859 A CN 112261859A CN 202011124548 A CN202011124548 A CN 202011124548A CN 112261859 A CN112261859 A CN 112261859A
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- H—ELECTRICITY
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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
- H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/085—Oxides of iron group metals
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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Abstract
A novel electromagnetic shielding material and a preparation method thereof belong to the technical field of high-performance shielding materials. The novel electromagnetic shielding material comprises a carbon nano tube aerogel film, a first shielding layer and a second shielding layer which are sequentially arranged, wherein the first shielding layer is nano silver, and the second shielding layer is cobalt, nickel or ferroferric oxide. According to the invention, the carbon nanotube is prepared into the film-forming structural aerogel, the aerogel is used as a framework, and the surface of the carbon nanotube is plated with the shielding material, so that the high-performance electromagnetic shielding coiled material is prepared.
Description
Technical Field
The invention relates to a technology in the field of high-performance shielding materials, in particular to a novel electromagnetic shielding material and a preparation method thereof.
Background
In the prior art, the electromagnetic shielding material is usually prepared by taking rigid solid, rubber or other high polymer materials as a matrix, taking metal, metal oxide and carbon as fillers and blending the materials in various ways. The heavy metal or metal oxide as the filler brings the defects of heavy finished product quality, secondary interference of electromagnetic waves and the like, and the filler of a single system causes narrow electromagnetic shielding absorption band.
At present, in order to solve the problems of narrow electromagnetic shielding absorption frequency band, poor electromagnetic shielding effectiveness and the like, a method for blending various systems is proposed by most scientific researchers, for example, a Chinese patent application with the application number of 201911263739.0 proposes to compound lignin, epoxy acrylate, carbon nano tubes and nano ferroferric oxide to prepare a novel electromagnetic shielding material, and the problems of narrow electromagnetic shielding frequency and poor electromagnetic shielding effect are solved. The Chinese patent application with the application number of 202010339384.5 proposes that metal-plated carbon fibers, alloy powder and silver-plated carbon nanotubes are added into matrix resin, and an electromagnetic shielding composite material is prepared through extrusion granulation, so that the problems of poor electromagnetic shielding effect, low tensile strength and the like in the prior art are solved.
However, the base material in the existing shielding material is generally low in conductivity or is an insulating substance, and the shielding effectiveness of the material is seriously reduced.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel electromagnetic shielding material and a preparation method thereof.
The invention relates to a novel electromagnetic shielding material, which comprises a carbon nano tube aerogel film, a first shielding layer and a second shielding layer which are sequentially arranged, wherein the first shielding layer is nano silver, and the second shielding layer is cobalt, nickel or ferroferric oxide.
Preferably, the carbon nanotube aerogel film has a thickness of 80-1600 μm and a density of 0.01-0.3g/cm3。
Preferably, the first shielding layer has a thickness of 10-50 nm.
Preferably, the weight ratio of the second shielding layer material to the carbon nanotubes is 2-20: 1.
the invention relates to a preparation method of the novel electromagnetic shielding material, which comprises the following steps:
s1, adding the carbon nano tube, the dispersing agent and water into a vacuum mixer according to a certain weight proportion, and stirring to prepare a carbon nano tube water-based gel liquid;
s2, coating a layer of carbon nanotube water-based gel liquid on the surface of the transfer substrate, transferring the carbon nanotube water-based gel liquid to a liquid nitrogen freeze-drying chamber along with the transfer substrate, and forming a carbon nanotube aerogel precursor on the surface of the transfer substrate;
s3, conveying the carbon nanotube aerogel precursor to a carbonization furnace along with the conveying base material, and sintering and carbonizing to obtain a carbon nanotube aerogel film;
s4, introducing the carbon nanotube aerogel film into vacuum sputtering equipment, sequentially depositing a first shielding layer and a second shielding layer, and finally continuously rolling to obtain a novel electromagnetic shielding material coiled material; the carbon nanotube aerogel film is peeled from the transfer substrate prior to entering the vacuum sputtering apparatus.
Preferably, the weight ratio of the carbon nanotubes to the dispersant to the water is 1: 1-10: 10-200, and the dispersing agent is PVA and/or PVP.
Preferably, the carbon nanotubes have a diameter of 10 to 200nm and a length of 5 to 20 μm.
In step S2, the thickness of the coating is 100-2000 μm.
Preferably, the temperature of the carbonization furnace is 100-800 ℃, and the continuous nitrogen protection is carried out.
Preferably, the transfer substrate is a thin metal sheet, typically aluminum foil or copper foil, selected according to the process requirements, and the transfer rate of the transfer substrate is 0.1-1 m/min.
Preferably, the walking time in the liquid nitrogen freeze drying chamber is 1-2h, and the walking time in the carbonization furnace is 1-4 h.
Technical effects
Compared with the prior art, the invention has the following technical effects:
1) electromagnetic waves are structurally absorbed through the carbon nanotube aerogel conductive network structure, the electronic energy level of the nano particles can be split due to the quantum size effect of the nano material, induction is generated on the electromagnetic waves with different wavelengths, and the absorption of the electromagnetic waves with different response frequencies is enhanced; the carbon nano tube in the aerogel has good electrical conductivity, and electromagnetic waves generate a huge reflection effect on the surface of the carbon nano tube; the surface of the carbon nano tube aerogel is plated with nano silver, a mixed interface is formed between the carbon nano tube aerogel and the nano silver for scattering, the reflection frequency band of electromagnetic waves is increased, incident electromagnetic waves form multiple reflection when passing through multiple interfaces, multiple energy consumption is generated, and the shielding efficiency and the absorption frequency bandwidth of the material are improved; in practical application, the carbon nanotube aerogel and the nano silver not only increase the conduction current and the inductive reactance loss, but also increase the energy consumption caused by multiple reflections due to a hybrid structure; the cobalt, nickel and ferroferric oxide coatings have complex magnetic permeability and complex dielectric constant, and can generate magnetic loss and dielectric loss for electromagnetic waves;
2) the carbon nano tube, the nano silver and the nickel/ferroferric oxide have excellent small-size effect and surface effect, when the attenuation of electromagnetic waves reaches a higher value, the reflection and absorption of the electromagnetic waves between the inner interface layers of the material are increased, the absorption frequency bandwidth and the absorption efficiency of the electromagnetic shielding material to the electromagnetic waves are improved, and the secondary interference can be effectively reduced; the conductive coating does not contain insulating substances and has good conductivity;
3) simple process, continuous production, controllable thickness of finished products and low surface density.
Drawings
Fig. 1 is an SEM photograph of the surface-silvered carbon nanotube aerogel in example 1;
FIG. 2 is an SEM photograph of the novel electromagnetic shielding material in example 1;
FIG. 3 is a schematic view illustrating a process for preparing an electromagnetic shielding material;
in the figure: the device comprises a vacuum mixer 1, a liquid nitrogen freeze-drying chamber 2, a carbonization furnace 3, a vacuum sputtering device 4 and an aluminum foil 5.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description. The experimental procedures, in which specific conditions are not specified in the examples, were carried out according to the conventional methods and conditions.
Example 1
The novel electromagnetic shielding material prepared by the system shown in fig. 3 comprises the following steps:
s1, mixing the components in a weight ratio of 1: 2: 100, adding the carbon nano tube, PVA and water into a vacuum mixer 1, and stirring to prepare a carbon nano tube water-based gel liquid;
s2, coating a layer of carbon nanotube water-based gel liquid with the thickness of 500 mu m on the surface of the aluminum foil 5 through a spray head, conveying the carbon nanotube water-based gel liquid to a liquid nitrogen freeze-drying chamber 2 along with the aluminum foil at the speed of 0.1m/min, and walking for 2 hours to obtain a carbon nanotube aerogel precursor;
s3, conveying the carbon nanotube aerogel precursor into a carbonization furnace 3 through aluminum foil, protecting with nitrogen, sintering and carbonizing at 300 ℃, and walking for 2 hours to obtain a carbon nanotube aerogel film;
s4, the carbon nanotube aerogel film is introduced into a vacuum sputtering device 4, and silver (shown in the SEM picture of figure 1, the silver is uniformly dispersed on the surface of the carbon nanotube) as a first shielding layer with the thickness of 100nm and the deposition density of 100g/dm are sequentially deposited3The second shielding layer of ferroferric oxide is finally continuously rolled to obtain the novel electromagnetic shielding material coiled material; before entering the vacuum sputtering equipment, the carbon nano tube aerogel film is peeled from the aluminum foil.
The prepared novel electromagnetic shielding material has the thickness of 500 mu m and the density of 225g/dm3The areal density of the alloy is 112.5g/m2And the SEM photograph is shown in figure 2, and ferroferric oxide is coated and filled in the aerogel in the form of particles.
Example 2
The novel electromagnetic shielding material prepared by the system shown in fig. 3 comprises the following steps:
s1, mixing the components in a weight ratio of 1: 4: 100, adding the carbon nano tube, PVP and water into a vacuum mixer 1, and stirring to prepare a carbon nano tube water-based gel liquid;
s2, coating a layer of carbon nanotube water-based gel liquid with the thickness of 300 mu m on the surface of the aluminum foil 5 through a spray head, conveying the carbon nanotube water-based gel liquid to a liquid nitrogen freeze-drying chamber 2 along with the aluminum foil at the speed of 0.1m/min, and walking for 2 hours to obtain a carbon nanotube aerogel precursor;
s3, conveying the carbon nanotube aerogel precursor into a carbonization furnace 3 through aluminum foil, protecting with nitrogen, sintering and carbonizing at 500 ℃, and walking for 2 hours to obtain a carbon nanotube aerogel film;
s4, introducing the carbon nano tube aerogel film into vacuum sputtering equipment 4, sequentially depositing a first shielding layer silver with the thickness of 50nm and a second shielding layer nickel with the thickness of 80g, and finally continuously rolling to obtain a novel electromagnetic shielding material coiled material; before entering the vacuum sputtering equipment, the carbon nano tube aerogel film is peeled from the aluminum foil.
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. The novel electromagnetic shielding material is characterized by comprising a carbon nano tube aerogel film, a first shielding layer and a second shielding layer which are sequentially arranged, wherein the first shielding layer is nano silver, and the second shielding layer is cobalt, nickel or ferroferric oxide.
2. The novel electromagnetic shielding material as claimed in claim 1, wherein the carbon nanotube aerogel film has a thickness of 80-1600 μm and a density of 0.01-0.3g/cm3。
3. The novel electromagnetic shielding material of claim 1, wherein the thickness of the first shielding layer is 10-50 nm.
4. The novel electromagnetic shielding material of claim 1, wherein the weight ratio of the second shielding layer material to the carbon nanotubes is 2-20: 1.
5. the preparation method of the novel electromagnetic shielding material is characterized by comprising the following steps of:
s1, adding the carbon nano tube, the dispersing agent and water into a vacuum mixer according to a certain weight proportion, and stirring to prepare a carbon nano tube water-based gel liquid;
s2, coating a layer of carbon nanotube water-based gel liquid on the surface of the transfer substrate, transferring the carbon nanotube water-based gel liquid to a liquid nitrogen freeze-drying chamber along with the transfer substrate, and forming a carbon nanotube aerogel precursor on the surface of the transfer substrate;
s3, conveying the carbon nanotube aerogel precursor to a carbonization furnace along with the conveying base material, and sintering and carbonizing to obtain a carbon nanotube aerogel film;
s4, introducing the carbon nanotube aerogel film into vacuum sputtering equipment, sequentially depositing a first shielding layer and a second shielding layer, and finally continuously rolling to obtain a novel electromagnetic shielding material coiled material; the carbon nanotube aerogel film is peeled from the transfer substrate prior to entering the vacuum sputtering apparatus.
6. The method for preparing a novel electromagnetic shielding material according to claim 5, wherein the weight ratio of the carbon nanotubes, the dispersant and the water is 1: 1-10: 10-200, and the dispersing agent is PVA and/or PVP.
7. The method for preparing a novel electromagnetic shielding material according to claim 5, wherein the carbon nanotubes have a diameter of 10 to 200nm and a length of 5 to 20 μm.
8. The method for preparing a novel electromagnetic shielding material as claimed in claim 5, wherein the coating thickness is 100-2000 μm in step S2.
9. The method for preparing a novel electromagnetic shielding material as claimed in claim 5, wherein the temperature of the carbonization furnace is 100 ℃ and 800 ℃, and the continuous nitrogen protection is performed.
10. A method for preparing a novel electromagnetic shielding material as claimed in claim 5, wherein the transfer rate of the transfer substrate is 0.1 to 1m/min, the traveling time in the liquid nitrogen freeze-drying chamber is 1 to 2 hours, and the traveling time in the carbonization furnace is 1 to 4 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103921520A (en) * | 2014-04-17 | 2014-07-16 | 苏州捷迪纳米科技有限公司 | Carbon nano tube film composite material and preparation method thereof |
| CN105273689A (en) * | 2014-07-18 | 2016-01-27 | 广东工业大学 | Novel multi-element structure composite conductive filling material |
| CN109526193A (en) * | 2018-11-07 | 2019-03-26 | 深圳科诺桥科技股份有限公司 | Electromagnetic shielding film and preparation method thereof |
| CN109591391A (en) * | 2018-11-08 | 2019-04-09 | 中北大学 | A kind of high shielding gradient-structure foamed material of low reflection |
| CN209652218U (en) * | 2019-02-25 | 2019-11-19 | 苏州义铠轩电子科技有限公司 | Nickel plating copper foil shielding tape |
| JP2020158866A (en) * | 2019-03-28 | 2020-10-01 | 芝浦メカトロニクス株式会社 | Film deposition apparatus |
-
2020
- 2020-10-20 CN CN202011124548.9A patent/CN112261859B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103921520A (en) * | 2014-04-17 | 2014-07-16 | 苏州捷迪纳米科技有限公司 | Carbon nano tube film composite material and preparation method thereof |
| CN105273689A (en) * | 2014-07-18 | 2016-01-27 | 广东工业大学 | Novel multi-element structure composite conductive filling material |
| CN109526193A (en) * | 2018-11-07 | 2019-03-26 | 深圳科诺桥科技股份有限公司 | Electromagnetic shielding film and preparation method thereof |
| CN109591391A (en) * | 2018-11-08 | 2019-04-09 | 中北大学 | A kind of high shielding gradient-structure foamed material of low reflection |
| CN209652218U (en) * | 2019-02-25 | 2019-11-19 | 苏州义铠轩电子科技有限公司 | Nickel plating copper foil shielding tape |
| JP2020158866A (en) * | 2019-03-28 | 2020-10-01 | 芝浦メカトロニクス株式会社 | Film deposition apparatus |
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