CN109022638B - Low-reflection and high-absorption electromagnetic shielding material and preparation method thereof - Google Patents
Low-reflection and high-absorption electromagnetic shielding material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
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Abstract
The invention discloses a low-reflection and high-absorption electromagnetic shielding material and a preparation method thereof, the electromagnetic shielding material is prepared by filling materials with high electromagnetic wave absorption and attenuation performance (including electric loss type nano metal particles, magnetic loss type nano metal particles and conductive high polymer) in natural leather by using natural leather (sheepskin, cowhide and pigskin) made from skins of livestock and animals as a base material through processes of retanning, in-situ polymerization, coating and the like, and then coating the materials on the surface of the leather by using a conductive material, thereby improving the electromagnetic wave absorption performance of the existing electromagnetic wave shielding leather. The electromagnetic shielding material prepared by the method has extremely high electromagnetic wave absorption performance, can adjust the absorption strength of electromagnetic waves according to requirements, and has simple preparation process.
Description
Technical Field
The invention belongs to the technical field of functional leather and preparation thereof, and particularly relates to a preparation method of low-reflection and high-absorption electromagnetic shielding leather.
Background
With the rapid development of modern electronic technology and the wide application of wireless communication equipment, electromagnetic radiation brings about increasingly serious problems of electromagnetic pollution, electromagnetic interference, information disclosure and the like (Wen, b.; Cao, m.s.; Lu, m.m.; et al. Reduced graphene oxides: Light-weight and high-efficiency electronic interference at estimated temperature [ J]Advanced Materials, 2014, 26(21): 3484-. According to statistics, the electromagnetic energy in the world space is increased by 7% -14% on average each year (the biological effect of electromagnetic radiation of Zhang Su Hui, the high degree of the vital line [ J ]]Safety and electromagnetic compatibility 2002 (6): 49-52.) long-term and excessive electromagnetic radiation can cause damage to human reproductive, visual, nervous and immune systems, and the like, and greatly endanger life (Wangjianzhi, Jujiezhi, Chonghao, and the like]Material guide, 2013, 7: 51-54). At present, the shielding mechanism of the conventional metal-based electromagnetic shielding material is reflection loss (SE)R) Mainly (Zhang, J.J.; Li, J.W.; Tan, G.G.; et al, Thin and flexible Fe-Si-B/Ni-Cu-P metallic glass multilayered compositions for electronic imaging sensing shielding [ J.]ACS appl. Mater. Interfaces, 2017, 9, 42192-A) Weak electromagnetic waves reflected back to the space cause secondary pollution and harm to the userThe human body is healthy. Therefore, development of a low-reflection, high-absorption wearable electromagnetic shielding material is demanded.
The low-reflection and high-absorption electromagnetic shielding material is a novel electromagnetic shielding material which can absorb most of electromagnetic waves and has little reflection. The electromagnetic wave energy is absorbed and converted into other forms of energy such as heat energy and the like to be emitted, so that the aim of electromagnetic shielding is fulfilled. In order to meet the requirements of low reflection and high absorption, the surface conductivity of the shielding material is required to be low, the wave impedance is matched with air as much as possible, and the reflection of electromagnetic waves on the surface of the shielding body is reduced; the most critical factor is to improve the loss performance of the shield against electromagnetic waves as much as possible. The loss mechanism of electromagnetic wave according to the material can be divided into two types, namely, electric loss type and magnetic loss type, and the electric loss type can be further divided into resistance loss type and dielectric loss type. The resistive loss type material mainly absorbs electromagnetic waves through the interaction with an electric field, most of the electromagnetic wave energy is attenuated on the resistance of the material, such as conductive nano metal, conductive high polymer and the like, which belong to the resistance type (Guo, J. L.; Wang, X. L.; Liao, X. P.; et al. Skin collagen fiber-biological synthesized of size-porous fibrous nanoparticles with light and high-density reactive microwave properties [ J. J. reactive microwave properties ] and the like]Study on electromagnetic parameters and wave-absorbing properties of J, Phys, chem, C, 2012, 116, 8188-8195, Yanhai swallow, Chen satellite, kou kai chang, protonic acid doped polyaniline [ J]Study on wave-absorbing performance of polypyrrole doped with sodium dodecyl benzene sulfonate [ J ] John's wort, Yaojianhua, Huangmenlong, No. 630-633, Gaojinwei, Yaojianfang, Huangmenlong, Sichuan]Research on electromagnetic parameters and wave-absorbing properties of material reporters, 2010, 24 (24), 9-12 Yanhai swallow, aged satellite, kou kaichang proton acid doped polyaniline [ J]Journal of the university of west ampere, 2011, 31(7), 630-; dielectric loss type materials absorb electromagnetic waves mainly by the effects of dielectric electron polarization, molecular polarization or interface polarization, etc., barium titanate, silicon carbide, silicon nitride, etc. are typical representatives thereof (royal hong, lao jiaxuan, panda, etc.. BaFe12O19/BaTiO3Preparation of composite Material and microwave Properties [ J ]]Rare metal materials and engineering, 2009, 38, 483-486 Luo Fa, Zhou Wancheng, jiao LianStudy on wave-absorbing properties of SiC (N)/LAS wave-absorbing material [ J]Inorganic materials bulletin, 2003, 18(3), 581-585 Zhao Donglin, Luo Fa, Wenwawang City nano silicon carbide, silicon nitride and silicon carbide powder doped with nitrogen and its microwave dielectric property [ J]The silicate bulletin, 2008, 36(6), 783-); magnetic loss type materials mainly absorb and attenuate electromagnetic waves by various mechanisms such as hysteresis loss, domain wall resonance loss, ferromagnetic resonance loss, eddy current loss, and The like, and mainly comprise ferrite, carbonyl iron, magnetic ultrafine metal powder, polycrystalline iron fiber, and The like (Nie, Y.; He, H.; Gong, R. Z.; et al. The electromagnetic characteristics and design of magnetic alloy Fe-Co composites for electromagnetic-wave absorber]. J. Magn. Magn. Mater., 2007, 310, 13-16. Feng, Y. B.; Qiu, T. Enhancement of electromagnetic and microwave absorbing properties of gas atomized Fe-50wt% Ni alloy by shape modification[J]J. Magn. Mater, 2012, 324, 2528-2533 Qiu Qin, Zyanqing, Zhanxiong, spinel type nano ferrite preparation and wave absorbing performance [ J]Material science and engineering, 2009, 27(5), 713-.
At present, the low reflection and high absorption electromagnetic wave shielding material is mainly prepared by compounding an electric loss type and/or magnetic loss type material with a high molecular polymer matrix to prepare a plate, foam, rubber or ceramic (guanshang, huangwanxia, maojian, etc.. research on low reflection and high absorption gradient electromagnetic wave shielding composite material [ J ]. functional material, 2003, 6(34), 676-. Although this kind of material solves the problem of electromagnetic environmental pollution caused by secondary reflection in most shielding materials to some extent, it does not have the characteristics of being soft and wearable.
Natural leather is a natural dielectric material, and has dielectric loss characteristics, and can convert part of electromagnetic wave energy into heat energy for dissipation through dipole polarization. At present, there has been a study on the preparation of an electromagnetic shielding leather by surface-coating a powder conductive material using natural leather as an absorption type substrate (patent No. ZL 201510704)631.6), the surface conductivity of the electromagnetic shielding type natural leather can be as high as 1.21 x 105S/m, the Shielding performance (SE) of the electromagnetic Shielding leather in an X wave band (8-12 GHz) is 90 dB, but the absorption loss (SE) of the electromagnetic Shielding leather is 90 dBA) Lower, absorption loss in shielding performance (SE)A%) is only 40%, indicating that most of the electromagnetic waves are reflected back to free space causing secondary pollution.
Based on the above analysis, it is an urgent need in the industry to better achieve the electromagnetic radiation protection of human body by constructing a low conductivity impedance matching layer on the surface of the natural leather and introducing a material with high absorption and attenuation performance to electromagnetic waves into the natural leather to effectively attenuate the energy of the electromagnetic waves so as to enhance the absorption loss of the natural leather to the electromagnetic waves and thus obtain an electromagnetic wave shielding material with low reflection, high absorption and good flexibility.
Disclosure of Invention
In view of the above-mentioned shortcomings, the present invention provides an electromagnetic wave shielding material for better protecting human body from electromagnetic radiation, which effectively attenuates electromagnetic wave energy by constructing a low-conductivity impedance matching layer on the surface of natural leather and introducing a material having high absorption and attenuation properties for electromagnetic waves into the natural leather, so as to enhance the absorption loss of the natural leather for electromagnetic waves, thereby obtaining an electromagnetic wave shielding material with low reflection, high absorption and good flexibility, and the preparation method of the material comprises the following steps:
(1) the method for preparing the high-absorption leather comprises the following steps: taking the natural leather, and then carrying out the steps of,
a. a method of bringing nano metal particles into natural leather (introducing electrically lossy nano metal particles and/or magnetically lossy nano metal particles into the interior of natural leather) through a carrier; or
b. A method of allowing metal ions to enter the interior of the natural leather before reduction (introducing a simple metal substance into the interior of the natural leather); or
c. A method of firstly leading the conductive high molecular monomer to enter the natural leather and then adding an initiator for in-situ polymerization (leading the conductive high molecular polymer into the natural leather);
obtaining high-absorption leather for later use;
(2) and (3) coating the nano conductive material on the surface of the high-absorption leather obtained in the step (1) to obtain the low-reflection high-absorption electromagnetic shielding material.
Furthermore, the natural leather is leather produced by taking cow leather, sheep leather or pig leather as a raw material according to a conventional leather-making method, and comprises leather produced by chrome tanning and other tanning methods.
Further, the carrier comprises plant tannin and absolute ethyl alcohol.
Further, the nano metal particles are electric loss type nano metal particles and/or magnetic loss type nano metal particles; the electric loss type nano metal particles comprise nano silver and nano copper; the magnetic loss type nano metal particles comprise nano ferroferric oxide and nano nickel.
Further, the metal ions include Ag+、Cu2+、Co2+、Ni2+。
Further, the reducing agent used in the step of reducing the metal ions entering the interior of the natural leather is selected from one or more of vegetable tannin, sodium borohydride, hydrazine hydrate and sodium hypophosphite.
Further, the conductive polymer monomer comprises one or more of pyrrole, aniline, thiophene and the like.
Further, the initiator is selected from one or more of ferric trichloride, ammonium persulfate and potassium persulfate.
Further, the nano conductive material is selected from one or more of nano silver-coated copper, nano silver, nano copper, graphene, carbon nano tube and the like.
In the invention, the film forming agent for coating the nano conductive material on the surface of the high-absorption leather comprises polyacrylate, polyurethane and epoxy resin.
The invention has the following advantages:
1. the invention endows the natural leather with the magnetic loss or/and resistance type dielectric loss performance to electromagnetic waves for the first time. The magnetic loss or/and resistance type dielectric loss property is not endowed to the collagen fibers, but the capability of losing electromagnetic waves is endowed to the whole natural leather by uniformly dispersing the magnetic loss or/and resistance type dielectric loss material among the collagen fibers. Collagen fibers are loose powders that do not have the wearable properties of natural leather.
2. The electric loss type nanometer metal particles, the magnetic loss type nanometer metal particles and the conductive high molecular polymer are introduced into the natural leather by a carrier method, or a method of firstly enabling metal ions to enter the natural leather and then reducing the metal ions, or a method of firstly enabling the conductive high molecular monomer to enter the natural leather and then adding an initiator for polymerization, so that the dielectric loss and the magnetic loss of the natural leather are enhanced, and the electromagnetic wave absorption performance of the natural leather is greatly improved. In the process, the mild plant tannin is selected as a reducing agent, and the ferric trichloride solution with the pH =3 is configured as an initiator, so that the natural leather can not be damaged due to strong redox reaction in the reaction process, and the wearability of the natural leather is ensured.
3. The electromagnetic shielding leather has the shielding mechanism of low reflection and high absorption, and can effectively relieve the secondary pollution problem of electromagnetic waves to the environment while remarkably improving the shielding efficiency. The reflection of the natural leather to the electromagnetic waves is reduced, the dosage of the coating conductive material is not simply reduced, but is controlled within an ideal range, the conductive layer can be formed to generate resistance loss to the electromagnetic waves, and good impedance matching can be realized with air, so that the purposes of low reflection and high absorption are achieved.
4. The raw materials used in the invention are all commercial products, are simple and easy to obtain, do not need to change a tanning process, and can be produced in a large scale.
Drawings
FIG. 1 shows the shielding effectiveness of low-reflection, high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-18 GHz.
FIG. 2 shows the absorption loss ratio of the low-reflection and high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-18 GHz.
FIG. 3 shows the shielding effectiveness of the low-reflection, high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-8 GHz.
FIG. 4 shows the absorption loss ratio of the low-reflection and high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-8 GHz.
FIG. 5 shows the shielding effectiveness of the low-reflection, high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-6 GHz.
FIG. 6 shows the absorption loss ratio of the low-reflection and high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-6 GHz.
FIG. 7 shows the shielding effectiveness of the low-reflection, high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-12 GHz.
FIG. 8 shows the absorption loss ratio of the low-reflection and high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 2-12 GHz.
FIG. 9 shows the shielding effectiveness of the low-reflection, high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 12-18 GHz.
FIG. 10 shows the absorption loss ratio of the low-reflection high-absorption electromagnetic shielding leather in the electromagnetic wave frequency range of 12-18 GHz.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the present invention is only used for further illustration, but the content of the present invention is not limited to the content of the examples, and the content of the present invention should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations based on the content of the present invention described above.
Example 1
Low-reflection and high-absorption electromagnetic shielding leather
The method for manufacturing the low-reflection and high-absorption electromagnetic shielding material based on the natural leather is characterized by comprising the following steps of:
the method for manufacturing the high-absorption electromagnetic shielding material based on the natural leather is characterized by comprising the following steps and conditions:
(1) taking natural leather with a certain size, taking plant tannin as a carrier, and introducing magnetic nano ferroferric oxide particles accounting for 20% of the weight of wet leather into the natural leather;
(2) coating the surface of the high-absorption leather obtained in the step (1) with nano silver-coated copper powder, wherein the dosage of the nano silver-coated copper powder is 6 mg cm-2And obtaining the low-reflection and high-absorption electromagnetic shielding leather.
As shown in FIGS. 1 and 2, the surface conductivity of the low-reflection, high-absorption electromagnetic shielding leather is 7.89X 102S/m, Shielding Effectiveness (SE) exceeding 60 dB in the frequency range of 2-18GHz, wherein absorption loss ratio (SE)A%) exceeds 80%.
Example 2
Low-reflection and high-absorption electromagnetic shielding leather
The method for manufacturing the low-reflection and high-absorption electromagnetic shielding material based on the natural leather is characterized by comprising the following steps of:
(1) taking natural leather with a certain size, introducing pyrrole monomers accounting for 10% of the weight of wet leather into the natural leather, adding an initiator ferric trichloride, and carrying out polymerization reaction at 0-5 ℃ for 30-60 min to generate conductive polypyrrole;
(2) coating graphene
The amount of graphene on the surface of the high-absorption leather obtained in the step (1) is 2 mg cm-2And obtaining the low-reflection and high-absorption electromagnetic shielding leather.
As shown in FIGS. 3 and 4, the surface conductivity of the low-reflection, high-absorption electromagnetic shielding leather is 8.96X 102S/m, a total Shielding Effectiveness (SE) of more than 40 dB in the frequency range of 2-8GHz, wherein the absorption losses (SE)A) The ratio of (A) to (B) exceeds 80%.
Example 3
Low-reflection and high-absorption electromagnetic shielding leather
The method for manufacturing the low-reflection and high-absorption electromagnetic shielding material based on the natural leather is characterized by comprising the following steps of:
(1) taking natural leather with a certain size, and 20% of Ag by weight of wet leather+Mixing with vegetable tannin, and retanningPutting into natural leather, and performing reduction reaction at 60-80 deg.C for 60 min;
(2) coating silver-coated copper powder on the surface of the high-absorption leather obtained in the step (1), wherein the using amount of the silver-coated copper powder is 4 mg cm-2And obtaining the low-reflection and high-absorption electromagnetic shielding leather.
As shown in FIGS. 5 and 6, the surface conductivity of the low-reflection, high-absorption electromagnetic shielding leather is 4.66X 102S/m, Shielding Effectiveness (SE) exceeding 60 dB in the frequency range of 2-6GHz, wherein absorption loss ratio (SE)A%) exceeds 50%.
Example 4
Low-reflection and high-absorption electromagnetic shielding leather
The method for manufacturing the low-reflection and high-absorption electromagnetic shielding material based on the natural leather is characterized by comprising the following steps of:
(1) taking natural leather with a certain size, taking plant tannin as a carrier, and introducing magnetic nano nickel particles accounting for 20% of the weight of wet leather into the natural leather;
(2) coating the nano silver powder on the surface of the high-absorption leather obtained in the step (1), wherein the dosage of the nano silver powder is 12 mg cm-2And obtaining the low-reflection and high-absorption electromagnetic shielding leather.
As shown in FIGS. 7 and 8, the surface conductivity of the low-reflection, high-absorption electromagnetic shielding leather was 6.77X 103S/m, a total Shielding Effectiveness (SE) of more than 30 dB in the frequency range of 2-18GHz, wherein the absorption losses (SE)A) The ratio of (A) to (B) exceeds 80%.
Example 5
Low-reflection and high-absorption electromagnetic shielding leather
The method for manufacturing the low-reflection and high-absorption electromagnetic shielding material based on the natural leather is characterized by comprising the following steps of:
(1) taking natural leather with a certain size, taking plant tannin as a carrier, and introducing nano silver particles accounting for 10% of the weight of wet leather into the natural leather;
(2) coating the silver-coated copper powder on the surface of the high-absorption leather obtained in the step (1),the dosage of the silver-coated copper powder is 4 mg cm-2And obtaining the low-reflection and high-absorption electromagnetic shielding leather.
As shown in FIGS. 9 and 10, the surface conductivity of the low-reflection, high-absorption electromagnetic shielding leather is 5.01X 102S/m, a total Shielding Effectiveness (SE) of more than 20 dB in the frequency range of 12-18GHz, wherein the absorption losses (SE)A) The ratio of (A) exceeds 40%.
Claims (10)
1. A preparation method of a low-reflection and high-absorption electromagnetic shielding material is characterized by comprising the following steps:
(1) the method for preparing the high-absorption leather comprises the following steps: taking the natural leather, and then carrying out the steps of,
a. a method of bringing nano metal particles into natural leather by a carrier; or
b. The method comprises the steps of firstly enabling metal ions to enter the interior of the natural leather and then reducing the metal ions; or
c. The method comprises the steps of firstly allowing a conductive high molecular monomer to enter the natural leather, and then adding an initiator for in-situ polymerization;
obtaining high-absorption leather for later use;
(2) and (3) coating the nano conductive material on the surface of the high-absorption leather obtained in the step (1) to obtain the low-reflection high-absorption electromagnetic shielding material.
2. The method of claim 1, wherein the natural leather is leather produced by conventional tanning methods using cow leather, sheep leather or pig leather as raw materials, including leather produced by chrome tanning and other tanning methods.
3. The method of claim 1, wherein the carrier comprises a plant tannin, absolute ethanol.
4. The production method according to claim 1, wherein the nanometal particles are electrically lossy nanometal particles and/or magnetically lossy nanometal particles; the electric loss type nano metal particles comprise nano silver and nano copper; the magnetic loss type nano metal particles comprise nano ferroferric oxide and nano nickel.
5. The method of claim 1, wherein the metal ions comprise Ag+、Cu2+、Co2+、Ni2+。
6. The preparation method according to claim 1, wherein the reducing agent used in the step of reducing the metal ions into the natural leather is one or more selected from vegetable tannin, sodium borohydride, hydrazine hydrate and sodium hypophosphite.
7. The method according to claim 1, wherein the conductive polymer monomer comprises one or more of pyrrole, aniline, and thiophene.
8. The preparation method according to claim 1, wherein the initiator is selected from one or more of ferric trichloride, ammonium persulfate and potassium persulfate.
9. The preparation method according to claim 1, wherein the nano conductive material is selected from one or more of nano silver-coated copper, nano silver, nano copper, graphene and carbon nano tube.
10. A low-reflection, high-absorption electromagnetic shielding material prepared by the preparation method according to any one of claims 1 to 9.
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| CN109880344B (en) * | 2019-01-30 | 2021-02-23 | 中北大学 | Preparation method of low-reflection high-shielding waterborne polyurethane electromagnetic shielding composite foam |
| CN110218823B (en) * | 2019-06-21 | 2021-07-23 | 四川大学 | high-Z element-natural leather composite X-ray shielding material and preparation method thereof |
| CN112646210B (en) * | 2019-10-11 | 2022-07-05 | 北京化工大学 | Collagen fiber-based electromagnetic shielding material with leather scraps as raw materials and preparation method thereof |
| CN110699962B (en) * | 2019-10-14 | 2022-07-08 | 浙江梅盛实业股份有限公司 | Preparation method of superfine fiber synthetic leather with electric heating function |
| CN115103586B (en) * | 2022-07-27 | 2024-07-02 | 成都理工大学 | Composite product with high conductivity and high electromagnetic shielding performance and preparation method thereof |
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| CN105658043A (en) * | 2014-11-10 | 2016-06-08 | 东华大学 | Electromagnetic shielding film material and preparation method thereof |
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| CN105658043A (en) * | 2014-11-10 | 2016-06-08 | 东华大学 | Electromagnetic shielding film material and preparation method thereof |
| CN106714537A (en) * | 2016-12-29 | 2017-05-24 | 四川大学 | Broadband electromagnetic wave shielding material and preparation method thereof |
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