CN115926434A - Layered polyurethane electromagnetic shielding composite foam and preparation method thereof - Google Patents
Layered polyurethane electromagnetic shielding composite foam and preparation method thereof Download PDFInfo
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- CN115926434A CN115926434A CN202310053049.2A CN202310053049A CN115926434A CN 115926434 A CN115926434 A CN 115926434A CN 202310053049 A CN202310053049 A CN 202310053049A CN 115926434 A CN115926434 A CN 115926434A
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000004814 polyurethane Substances 0.000 title claims abstract description 92
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 92
- 239000006260 foam Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000004005 microsphere Substances 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000005187 foaming Methods 0.000 claims abstract description 13
- 239000006249 magnetic particle Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011324 bead Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000011325 microbead Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 9
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- 238000001816 cooling Methods 0.000 claims description 8
- 238000009738 saturating Methods 0.000 claims description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 206010070834 Sensitisation Diseases 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000008313 sensitization Effects 0.000 claims description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002122 magnetic nanoparticle Substances 0.000 abstract 1
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000013012 foaming technology Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005670 electromagnetic radiation Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AYRXSINWFIIFAE-UHFFFAOYSA-N O6-alpha-D-Galactopyranosyl-D-galactose Natural products OCC1OC(OCC(O)C(O)C(O)C(O)C=O)C(O)C(O)C1O AYRXSINWFIIFAE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- DLRVVLDZNNYCBX-CQUJWQHSSA-N gentiobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-CQUJWQHSSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The invention discloses layered polyurethane electromagnetic shielding composite foam and a preparation method thereof, and belongs to the technical field of electromagnetic shielding materials. The method comprises the steps of firstly preparing solid glass microspheres loaded with conductive metal to obtain conductive microspheres, then mixing the conductive microspheres, magnetic nanoparticles and waterborne polyurethane, standing for layering, drying to obtain a polyurethane composite material, and finally foaming the polyurethane composite material to obtain the electromagnetic shielding composite foam. The method can improve the electromagnetic shielding performance while reducing the additive amount of the filler in the composite material, and the prepared material has good electromagnetic shielding and absorption performance under the condition of low filler content.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding materials, and particularly relates to layered polyurethane electromagnetic shielding composite foam and a preparation method thereof.
Background
Along with the continuous development of science and technology in recent years, a large amount of electronic equipment and small-size intelligent electronic terminals have entered people's life, and when these electronic products make things convenient for people's life, improve people's quality of life, another big class of pollution also produced along with it: electromagnetic radiation. Electromagnetic radiation not only can interfere electronic equipment and affect the normal use of the electronic equipment, but also can cause harm to human health if being in an electromagnetic radiation environment for a long time, so that the production of efficient electromagnetic interference (EMI) shielding materials is very important.
Although the traditional metal electromagnetic interference shielding material has excellent electromagnetic shielding performance, the defects of poor flexibility, high density, difficulty in processing, easiness in corrosion and the like are increasingly remarkable nowadays when portable electronic equipment and wearable miniature intelligent terminals are rapidly developed, and the requirements of the current society cannot be met, so that a novel electromagnetic shielding material capable of meeting the current requirements is urgently needed. In recent years, polymer-based electromagnetic shielding composite materials have attracted much attention due to the advantages of strong flexibility, easy processing, adjustable shielding performance and the like, but in order to obtain higher electromagnetic shielding performance, a large amount of filler is often required to be added into the composite materials, so that the density of the composite materials is increased, the mechanical performance is reduced, the processing difficulty and the manufacturing cost of the materials are improved, and the wider application of the composite materials is limited.
The high-pressure gas foaming technology can manufacture a large number of tiny foam holes in a polymer matrix, and the polymer electromagnetic shielding composite material is further processed by using the high-pressure gas foaming technology, so that the electromagnetic shielding performance of the material can be improved, the density of the material can be reduced, and raw materials can be saved. By means of a density induction method, the filler can be gathered at the bottom of the polyurethane matrix after the solvent is volatilized by utilizing the density difference between the filler and the solvent, and a conductive network can be constructed more efficiently to provide higher electromagnetic shielding performance. The polymer is added with magnetic particles, and electromagnetic waves can be effectively absorbed through absorption-reflection-absorption modes. At present, no research report on the preparation of the layered polyurethane electromagnetic shielding composite foam by a high-pressure gas foaming technology exists.
Disclosure of Invention
The invention aims to provide layered polyurethane electromagnetic shielding composite foam and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
s1: loading metal on the surface of the solid glass microsphere to obtain a conductive microsphere;
s2: preparing a layered polyurethane composite material containing conductive microspheres and magnetic particles;
s3: and (3) placing the composite material prepared by the S2 in foaming gas, saturating for 5min-24h at the temperature of 0-300 ℃ and under the pressure of 0.5-50MPa, then relieving pressure to normal pressure at the speed of 0.1-30MPa/S, and cooling to room temperature to obtain the electromagnetic shielding composite foam.
Further, the metal loaded on the conductive micro-beads is silver, copper, nickel, aluminum, iron or tungsten.
Further, the magnetic particles are iron nickel @ graphene, iron nickel @ carbon nanotubes, nickel cobalt @ graphene, nickel cobalt @ carbon nanotubes, iron cobalt @ graphene, iron cobalt @ carbon nanotubes, ferroferric oxide @ graphene or ferroferric oxide @ carbon nanotubes.
Further, the preparation of the conductive microbead comprises the following steps:
and (4) SS1: firstly, adding solid glass beads into a sensitizer for sensitization;
and (4) SS2: and adding the sensitized solid glass beads into a chemical plating solution (containing conductive metal ions) according to a material ratio of 1g to 5-100mL, then gradually adding a reducing agent solution, stirring for reaction for 5min-5h, washing and drying to obtain the conductive beads.
Further, the method for preparing the layered polyurethane composite material containing the conductive microspheres and the magnetic particles is a one-time blending casting method or a multiple casting method.
Further, the one-time blending casting method comprises the following steps: adding conductive microspheres and magnetic particles into waterborne polyurethane, ultrasonically stirring for 5-30min, pouring into a mold, standing for 5-30min for layering, then placing in a 60 ℃ oven for drying for 6-18h, and volatilizing a solvent to obtain a layered polyurethane composite material containing the conductive microspheres and the magnetic particles; the multiple casting method comprises the following steps: adding conductive microspheres into waterborne polyurethane, ultrasonically stirring for 5-30min, standing for 5-30min, pouring into a mold, standing for 5-30min, then drying in a 60 ℃ oven for 6-18h to obtain a conductive microsphere-polyurethane composite material, adding magnetic particles into waterborne polyurethane, ultrasonically stirring for 5-30min, then pouring a magnetic particle-polyurethane mixture on the upper layer of the conductive microsphere-polyurethane composite material, and drying in the 60 ℃ oven for 6-18h to obtain a layered polyurethane composite material containing the conductive microspheres and the magnetic particles.
Further, the mass ratio of the waterborne polyurethane to the conductive microspheres is 2:1-10; the mass ratio of the aqueous polyurethane to the magnetic particles is 2:1-10.
Further, the foaming gas is carbon dioxide, nitrogen, argon, helium, air, pentane, hexane, heptane, dichloromethane, dichloroethane, butane, n-pentane, n-hexane, n-heptane, petroleum ether, trichlorofluoromethane or ethane.
The invention adopts the high-pressure gas foaming technology and combines the density induction method to prepare the layered polyurethane electromagnetic shielding composite foam, the method effectively reduces the filler usage amount of the electromagnetic shielding composite material, improves the electric conduction and the electromagnetic shielding efficiency of the composite foam, the prepared foam material has good electric conduction performance under the condition of low conductive filler content, and the electromagnetic shielding efficiency can reach 42dB (the requirement of commercial application is 20 dB).
The invention has the beneficial effects that:
1. in the preparation of the layered polyurethane electromagnetic shielding composite foam, the selective dispersion of the conductive microspheres is realized by chemical plating and density induction methods, the lapping efficiency of the conductive microspheres in a polymer is improved, and the conductive network access is further perfected.
2. The electromagnetic wave shielding material adopts a layered structure, introduces magnetic particles to absorb electromagnetic waves, can effectively absorb the electromagnetic waves through the absorption-reflection-absorption process, improves the electromagnetic shielding performance, reduces the electromagnetic wave reflection and avoids secondary pollution. Meanwhile, the density of the material can be further reduced by introducing the foam holes, the shielding performance is improved by multiple reflection and absorption of the foam holes to electromagnetic waves, and the potential application field of the electromagnetic shielding material is widened.
3. The invention adopts the waterborne polyurethane as the matrix, uses the water as the solvent, does not need to use toxic and harmful organic solvents, and is safe, green and environment-friendly.
4. The foaming mode adopted by the invention is high-pressure gas foaming, and has the characteristics of low cost, simple operation, no solvent residue and uniform foam pores.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is (a) a scanning electron microscope image and (b) a silver mapping image of the metallic silver-supported solid glass beads prepared in example 6.
FIG. 2 is a scanning electron microscope image of a cross section of the layered polyurethane electromagnetic shielding composite foam prepared in example 6.
Fig. 3 is a graph showing the electrical conductivity of the layered polyurethane electromagnetic shielding composite foam prepared in examples 2, 4 and 6.
Fig. 4 shows the electromagnetic shielding performance of the layered polyurethane electromagnetic shielding composite foam prepared in example 6.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
(1) Preparation of conductive metal loaded solid glass micro-beads
Treating and washing 3g of solid glass microspheres by stannous chloride, adding the product into 15mL of chemical tungsten plating solution (20 g/L of sodium tungstate and 20g/L of sodium hypophosphite), dropwise adding 10mL of reducing solution (20 g/L of sodium citrate and 50g/L of ammonium sulfate), stirring and reacting for 5min, and performing suction filtration, washing and drying to obtain the metal tungsten-loaded solid glass microspheres.
(2) Preparation of layered polyurethane composite material containing conductive microspheres and magnetic particles
Adding 0.7g of metal tungsten loaded glass beads and 0.7g of iron-nickel @ graphene magnetic particles into 20mL of waterborne polyurethane, ultrasonically stirring for 5min, pouring the mixture into a mold, standing for 5min, and then placing the mold into a 60 ℃ oven to dry for 6h to obtain the layered polyurethane composite material containing the conductive beads and the magnetic particles.
(3) High pressure gas foaming
Cutting the obtained composite material into a regular shape, placing the composite material in a high-pressure reaction kettle, heating, introducing air, saturating for 5min at the temperature of 20 ℃ and the pressure of 0.5MPa, then relieving the pressure to the normal pressure at the speed of 0.1MPa/s, cooling to room temperature, taking out a sample, and obtaining the layered polyurethane electromagnetic shielding composite foam.
Example 2
A preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
(1) Preparation of conductive metal loaded solid glass microsphere
Treating and washing 3g of solid glass beads with stannous chloride, adding the product into 50mL of chemical iron plating solution (15 g/L of ferric sulfate and 2g/L of gentiobiose), dropwise adding 15mL of 1.5g/L sodium borohydride solution, stirring and reacting for 1h, and performing suction filtration, washing and drying to obtain the metallic iron loaded solid glass beads.
(2) Preparation of layered polyurethane composite material containing conductive microspheres and magnetic particles
Adding 1.4g of metallic iron-loaded glass beads into 10mL of waterborne polyurethane, ultrasonically stirring for 10min, pouring the mixture into a mold, standing for 10min, and then drying in a 60 ℃ drying oven for 10h to obtain the conductive bead-polyurethane composite material. Adding 1.4g of iron-nickel @ carbon nanotube magnetic particles into 10mL of waterborne polyurethane, ultrasonically stirring for 10min, pouring the mixture onto the upper surface of the conductive microsphere-polyurethane composite material, and drying in an oven at 60 ℃ for 10h to obtain the layered polyurethane composite material containing the conductive microspheres and the magnetic particles.
(3) High pressure gas foaming
Cutting the obtained composite material into a regular shape, placing the composite material in a high-pressure reaction kettle, heating, introducing ethane gas, saturating for 30min at the temperature of 70 ℃ and the pressure of 20MPa, then decompressing to normal pressure at the speed of 5MPa/s, cooling to room temperature, taking out a sample, and obtaining the layered polyurethane electromagnetic shielding composite foam.
Example 3
A preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
(1) Preparation of conductive metal loaded solid glass beads
Treating and washing 3g of solid glass microspheres with stannous chloride, adding the product into 100mL of chemical aluminum plating liquid (5 g/L of aluminum chloride and 25g/L of sodium hypophosphite), dropwise adding 20mL of 1g/L lithium hydride solution, stirring for reaction for 2 hours, and performing suction filtration, washing and drying to obtain the metal aluminum loaded solid glass microspheres.
(2) Preparation of layered polyurethane composite material containing conductive microspheres and magnetic particles
Adding 2.1g of metal aluminum loaded glass beads into 10mL of waterborne polyurethane, ultrasonically stirring for 15min, pouring the mixture into a mold, standing for 15min, and drying in a 60 ℃ drying oven for 12h to obtain the conductive bead-polyurethane composite material. Adding 2.1g of iron, cobalt and graphene magnetic particles into 10mL of waterborne polyurethane, ultrasonically stirring for 15min, pouring the mixture onto the upper surface of the conductive microsphere-polyurethane composite material, and drying in an oven at 60 ℃ for 12h to obtain the layered polyurethane composite material containing the conductive microspheres and the magnetic particles.
(3) High pressure gas foaming
Cutting the obtained composite material into a regular shape, placing the composite material in a high-pressure reaction kettle, heating, introducing nitrogen, saturating for 2min at 270 ℃ and 30MPa, then relieving pressure to normal pressure at the rate of 20MPa/s, cooling to room temperature, taking out a sample, and obtaining the layered polyurethane electromagnetic shielding composite foam.
Example 4
A preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
(1) Preparation of conductive metal loaded solid glass beads
Treating and washing 3g of solid glass microspheres with stannous chloride, adding the product into 200mL of chemical nickel plating solution (40 g/L of nickel sulfate, 10g/L of sodium pyrophosphate, 5g/L of sodium hypophosphite, 5g/L of thiourea and a proper amount of ammonia), dropwise adding 30mL of 15mL/L triethanolamine solution, stirring and reacting for 3 hours, and performing suction filtration, washing and drying to obtain the metallic nickel loaded solid glass microspheres.
(2) Preparation of layered polyurethane composite material containing conductive microspheres and magnetic particles
Adding 2.8g of metallic nickel-loaded glass beads and 2.8g of ferroferric oxide @ graphene into 20mL of waterborne polyurethane, ultrasonically stirring for 25min, pouring the mixture into a mold, standing for 25min, and drying in an oven at 60 ℃ for 14h to obtain the layered polyurethane composite material containing the conductive beads and the magnetic particles.
(3) High pressure gas foaming
Cutting the obtained composite material into a regular shape, placing the composite material in a high-pressure reaction kettle, heating, introducing carbon dioxide, saturating for 4 hours at 140 ℃ and 50MPa, then relieving pressure to normal pressure at the rate of 30MPa/s, cooling to room temperature, taking out a sample, and obtaining the layered polyurethane electromagnetic shielding composite foam.
Example 5
A preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
(1) Preparation of conductive metal loaded solid glass beads
Treating and washing 3g of solid glass microspheres with stannous chloride, adding the product into 300mL of chemical copper plating solution (50 g/L of copper chloride, 20g/L of disodium ethylenediamine tetraacetic acid and 1g/L of boric acid), dropwise adding 40mL of 1g/L dimethylamine borane solution, stirring and reacting for 5 hours, and performing suction filtration, washing and drying to obtain the metallic copper loaded solid glass microspheres.
(2) Preparation of layered polyurethane composite material containing conductive micro-beads and magnetic particles
Adding 3.5g of metal copper loaded glass beads into 10mL of waterborne polyurethane, ultrasonically stirring for 30min, pouring the mixture into a mold, standing for 30min, and drying in an oven at 60 ℃ for 16h to obtain the conductive bead-polyurethane composite material. Adding 3.5g of nickel cobalt @ carbon nanotube magnetic particles into 10mL of waterborne polyurethane, ultrasonically stirring for 30min, pouring the mixture onto the upper surface of the conductive microsphere-polyurethane composite material, and drying in a drying oven at 60 ℃ for 16h to obtain the layered polyurethane composite material containing the conductive microspheres and the magnetic particles.
(3) High pressure gas foaming
Cutting the obtained composite material into a regular shape, placing the regular shape in a high-pressure reaction kettle, heating, introducing n-pentane, saturating for 24 hours at the temperature of 300 ℃ and the pressure of 10MPa, then decompressing to normal pressure at the speed of 10MPa/s, cooling to room temperature, taking out a sample, and obtaining the layered polyurethane electromagnetic shielding composite foam.
Example 6
A preparation method of layered polyurethane electromagnetic shielding composite foam comprises the following steps:
(1) Preparation of conductive metal loaded solid glass beads
Treating and washing 3g of solid glass microspheres with stannous chloride, adding the product into 100mL of chemical silver plating solution (10 g/L of silver nitrate and 20mL/L of ammonia water), dropwise adding 20mL of reducing solution (250 g/L of potassium sodium tartrate, 25g/L of sodium hydroxide and 35g/L of glucose), stirring for reacting for 20min, and performing suction filtration, washing and drying to obtain the metal silver loaded solid glass microspheres.
(2) Preparation of layered polyurethane composite material containing conductive microspheres and magnetic particles
Adding 3.5g of metal silver loaded glass beads into 10mL of waterborne polyurethane, ultrasonically stirring for 20min, pouring the mixture into a mold, standing for 20min, and drying in an oven at 60 ℃ for 8h to obtain the conductive bead-polyurethane composite material. Adding 3.5g of iron, cobalt and graphene magnetic particles into 10mL of waterborne polyurethane, ultrasonically stirring for 20min, pouring the mixture onto the upper surface of the conductive microsphere-waterborne polyurethane composite material, and drying in an oven at 60 ℃ for 8h to obtain the layered polyurethane composite material containing the conductive microspheres and the magnetic particles.
(3) High pressure gas foaming
Cutting the obtained composite material into a regular shape, placing the composite material in a high-pressure reaction kettle, heating, introducing carbon dioxide gas, saturating for 1h at the temperature of 120 ℃ and the pressure of 10MPa, then decompressing to normal pressure at the speed of 5MPa/s, cooling to room temperature, taking out a sample, and obtaining the layered polyurethane electromagnetic shielding composite foam.
Analysis of results
By taking example 6 as an example, the sections of the metallic silver loaded solid glass microspheres and the composite foam are characterized by a scanning electron microscope, and the results are respectively shown in fig. 1 and fig. 2. The metal silver is loaded on the surface of the glass microsphere; the cross section of the composite foam can be seen to have good foam appearance, and the metal silver loaded solid glass microspheres are gathered on the lower surface of the composite foam, so that a conductive network is effectively formed.
FIG. 3 is the conductivity of example 2, example 4 and example 6; fig. 4 shows the electromagnetic shielding performance of example 6. It can be seen that the conductivity gradually increases as the content of the conductive microbeads increases; the electromagnetic shielding material has good electromagnetic shielding performance and absorption performance in the wave band of 8GHz to 12.4 GHz.
The above description of the embodiments specifically describes the analysis method according to the present invention. It should be noted that the above description is only for the purpose of helping those skilled in the art better understand the method and idea of the present invention, and not for the limitation of the related contents. The present invention may be appropriately adjusted or modified by those skilled in the art without departing from the principle of the present invention, and the adjustment and modification also fall within the scope of the present invention.
Claims (10)
1. The preparation method of the layered polyurethane electromagnetic shielding composite foam is characterized by comprising the following steps of:
s1: loading metal on the surface of the solid glass microsphere to obtain a conductive microsphere;
s2: preparing a layered polyurethane composite material containing conductive micro-beads and magnetic particles;
s3: and (3) placing the composite material prepared in the step (S2) in foaming gas, saturating for 5min-24h at the temperature of 0-300 ℃ and under the pressure of 0.5-50MPa, then decompressing to normal pressure at the speed of 0.1-30MPa/S, and cooling to room temperature to obtain the electromagnetic shielding composite foam.
2. The method for preparing the layered polyurethane electromagnetic shielding composite foam as claimed in claim 1, wherein the metal loaded on the conductive micro-beads is silver, copper, nickel, aluminum, iron or tungsten.
3. The method of claim 1, wherein the magnetic particles are iron-nickel @ graphene, iron-nickel @ carbon nanotubes, nickel-cobalt @ graphene, nickel-cobalt @ carbon nanotubes, iron-cobalt @ graphene, iron-cobalt @ carbon nanotubes, ferroferric oxide @ graphene, or ferroferric oxide @ carbon nanotubes.
4. The method for preparing the layered polyurethane electromagnetic shielding composite foam as claimed in claim 1, wherein the preparation of the conductive beads comprises the following steps:
and (4) SS1: firstly, adding solid glass beads into a sensitizer for sensitization;
and (4) SS2: and adding the sensitized solid glass beads into the chemical plating solution according to a material ratio of 1g to 5-100mL, then gradually adding a reducing agent solution, stirring for reaction for 5min-5h, and then washing and drying to obtain the conductive beads.
5. The method for preparing the layered polyurethane electromagnetic shielding composite foam as claimed in claim 1, wherein the method for preparing the layered polyurethane composite material containing the conductive micro-beads and the magnetic particles is a one-time co-pouring method or a multi-time pouring method.
6. The method for preparing the layered polyurethane electromagnetic shielding composite foam of claim 5, wherein the one-time co-casting method comprises the following steps: adding conductive micro-beads and magnetic particles into waterborne polyurethane, ultrasonically stirring for 5-30min, pouring into a mold, standing for 5-30min to stratify, then placing in a 60 ℃ drying oven for drying for 6-18h, and volatilizing a solvent to obtain the layered polyurethane composite material containing the conductive micro-beads and the magnetic particles.
7. The method for preparing the layered polyurethane composite foam for electromagnetic shielding of claim 5, wherein the multiple casting method comprises the following steps: adding conductive microspheres into waterborne polyurethane, ultrasonically stirring for 5-30min, standing for 5-30min, pouring into a mold, standing for 5-30min, then drying in a 60 ℃ drying oven for 6-18h to obtain a conductive microsphere-polyurethane composite material, adding magnetic particles into waterborne polyurethane, ultrasonically stirring for 5-30min, then pouring a magnetic particle-polyurethane mixture on the upper layer of the conductive microsphere-polyurethane composite material, and drying in the 60 ℃ drying oven for 6-18h to obtain a layered polyurethane composite material containing the conductive microspheres and the magnetic particles.
8. The preparation method of the layered polyurethane electromagnetic shielding composite foam according to claim 6 or 7, wherein the mass ratio of the aqueous polyurethane to the conductive beads is 2:1-10; the mass ratio of the aqueous polyurethane to the magnetic particles is 2:1-10.
9. The method for preparing the layered polyurethane electromagnetic shielding composite foam according to claim 1, wherein the foaming gas is carbon dioxide, nitrogen, argon, helium, air, pentane, hexane, heptane, dichloromethane, dichloroethane, butane, n-pentane, n-hexane, n-heptane, petroleum ether, trichlorofluoromethane or ethane.
10. A layered polyurethane electromagnetic shielding syntactic foam prepared by the method of any one of claims 1 to 7 or 9.
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