CN108165019A - A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material and preparation method thereof - Google Patents
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 277
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 154
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 107
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 88
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- 238000004513 sizing Methods 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 27
- 239000010439 graphite Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002048 multi walled nanotube Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000004945 silicone rubber Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000017 hydrogel Substances 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- -1 Graphite alkene Chemical class 0.000 claims description 6
- 239000004964 aerogel Substances 0.000 claims description 6
- 239000002079 double walled nanotube Substances 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
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- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 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 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 241001122767 Theaceae Species 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940067157 phenylhydrazine Drugs 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 238000013040 rubber vulcanization Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite materials and preparation method thereof.The composition of the composite material is：100 mass parts of silicon rubber, 0.05~1 mass parts of graphene, 0.01~0.5 mass parts of carbon nanotube.The structure feature of the composite material is：In the three-dimensional continuous conduction network skeleton that silicon rubber filling is constructed in graphene/carbon nano-tube in composite material, conducting matrix grain is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube.The preparation method of the composite material is：Three-dimensional continuous graphene/carbon nano-tube conductive network skeleton is first constructed, then backfills silicon rubber, vulcanization sizing again.The composite material realizes high conductivity and prominent capability of electromagnetic shielding under low sizing dosage (≤1.5wt%)：Conductivity is up to more than 100S/m, and the electromagnet shield effect under X-band (8.2~12.4GHz) is up to more than 35dB.
Description
Technical field
The present invention relates to electromagnetic shielding material fields, and in particular to a kind of electromagnetic shielding silicon rubber/graphene/carbon nanometer
Pipe nanocomposite and preparation method thereof.
Background technology
The features such as conductive rubber is due to good airproof performance, density is low, corrosion-resistant, easy processing molding, leads in electromagnetic shielding material
Very important status is occupied in domain.Conventional conductive rubber is by conductive fillers such as carbon-based material, metal material or metallizations
It is added in rubber matrix obtained.Compared with metal and metal-coated fillers, carbon system filler has at low cost, high temperature resistant, antioxygen
The advantages such as change, corrosion-resistant, lightweight, chemical stabilization, it is also relatively strong with the affinity of rubber matrix, conductive rubber can be assigned
Excellent mechanical property and the stability under complex environment【ACS Appl.Mater.Interfaces,2013,5,2677】.
But tradition carbon-based material (conductive black, carbon fiber and graphite) conductivity is low, it is difficult to which the height that conductivity is higher than l00S/m is made
Conductive rubber, it is impossible to meet the requirement that commercial electromagnet shielding material shield effectiveness is more than 20dB.With carbon nanotube and graphene
(conductivity is up to 105S/m appearance), carbon-based material have welcome new development opportunity in high electroconductive rubber Material Field.
Silicon rubber is as a kind of high reliability elastomeric material, because of its excellent resistant of high or low temperature, radiation resistance, ageing-resistant
Property and chemical resistance etc., are widely used in the high-technology fields such as aerospace, military equipment.By carbon nanotube and/
Or graphene is added to the high-conductivity silicon rubber nanocomposite for being expected to obtain high reliability in silicon rubber.However, at present
The conductivity overwhelming majority of silicon rubber/graphene (carbon nanotube) nanocomposite of report is in the 1S/m orders of magnitude, from the phase
The 100S/m orders of magnitude treated still have very big distance【CN 201610439997.X；Carbon,2009,47,922；
Adv.Funct.Mater.,2015,25,559】.Study carefully its main cause：First, most silicon rubber/graphene (carbon nanometers
Pipe) nanocomposite be by the conventional methods such as solution blending, emulsion blending or melt blending prepare, in prepared silicon rubber
In glue composite material, carbon nanotube or the graphene random distribution in silicone rubber matrix need higher volume fraction could shape
Into conductive path；And carbon nanotube or graphene are surrounded by matrix, cause the contact resistance between filler-filler very high, and then
The conductivity for leading to composite material is very low.In addition, it is nano combined to prepare silicon rubber/graphene (carbon nanotube) using conventional method
Material, the specific surface energy of the specific surface area and superelevation of carbon nanotube and graphene super large make it easily reunite in a polymer matrix
Or stack, it is difficult to form uniform conductive network.Although surface modification can improve carbon nanotube and graphene in polymer matrix
Dispersion in body, but destroy its intrinsic superior electrical conductivity.
The shortcomings that in order to overcome above-mentioned traditional polymer composite material and preparation method thereof, a few studies person use and first construct three-dimensional
" backfill method " method that polymeric matrix is perfused after conductive network prepares silicon rubber/graphene (carbon nanotube) nano combined material
Material.The conductive path of the composite material prepared by this method is directly to overlap the real three-dimensional conductive formed by filler-filler
Network significantly reduces the contact resistance between filler and filler, and it is compound can to significantly improve polymer under low sizing content
The conductivity of material【Chem.Commun.,2013,49,1612；Composites:Part A,2017,92,190】.For example,
Resorcinol and formaldehyde are dissolved in the aqueous dispersions of graphene oxide/acidification multi-walled carbon nanotube by Mengting Chen etc.,
Organogel is prepared for by the condensation of resorcinol and formaldehyde, it is more to have obtained acidification after freeze-dried and 1000 DEG C of heat treatments
Wall carbon nano tube/graphene/charcoal three-dimensional conductive network finally pours into silicon rubber performed polymer and vulcanizes to obtain silicon rubber nano composite wood
Material.When the content of graphene and multi-walled carbon nanotube is 1.3wt%, the conductivity of silicon rubber nano composite material is reachable
280S/m improves 4 compared with the conductivity (0.05S/m) of silicon rubber nano composite material prepared by solution blended process under same amount
A order of magnitude.However, the acidification of carbon nanotube and the presence of charcoal impurity can seriously damage the conductivity of conductive network
【Chem.Commun.,2013,49,1612】.Zongping Chen etc. are synthesized by chemical vapour deposition technique on nickel foam
Then graphene pours into silicon rubber performed polymer, nickel foam is etched away after silicon rubber vulcanization and obtains the nano combined material of porous silicone rubber
Material.When graphene content is~0.7wt%, the conductivity of composite material is up to 180S/m, in the electromagnetic screen of 30MHz~1.5GHz
Cover efficiency it is reachable~30dB.However, three-dimensional grapheme conductive network can be by partial destruction in metal foam etching process；And
Mechanical property, sealing performance of porosity meeting deep fades composite material of composite material etc.【Adv.Mater.,2013,25,
1296】.Similarly, Xinying Sun etc. have synthesized graphene by chemical vapour deposition technique on nickel foam, then pour into silicon
Rubber performed polymer/acidification multi-walled carbon nanotube mixture etches away nickel foam after silicon rubber vulcanization and obtains porous silicone rubber nanometer
Composite material.When graphene and acidification multi-walled carbon nanotube content are respectively 2.7wt% and 2.0wt%, the electricity of composite material
Conductance and electromagnet shield effect are respectively up to 3150S/m and 75dB.The composites are there are the above problem, and it is three-dimensional
Conductive network is mainly overlapped by graphene, and there is no play a role carbon nanotube completely【Composites:Part A,
2017,92,190】.So far, using graphene oxide and unmodified carbon nanotube as raw material, pass through simple sol-gel
Method constructs three-dimensional grapheme/carbon nano tube network, then backfills silicon rubber and prepares silicon rubber/graphene/carbon nano-tube nanometer
The research of composite material there is no report.
To sum up, the structural intergrity of three-dimensional conductive network and conductivity determine the conductivity and electromagnetic screen of final composite material
Cover efficiency.High Performance Shielding can be constructed out based on the three-dimensional continuous double conductive network skeletons of graphene/carbon nano-tube to use
Silicon rubber/graphene/carbon nano tube nanocomposite material.
Invention content
In view of the foregoing, the purpose of the present invention is to provide a kind of electromagnetic shielding silicon rubber/graphene/carbon nano-tubes
Nanocomposite and preparation method thereof.The composition of the composite material is：100 mass parts of silicon rubber, 0.05~1 mass of graphene
Part, 0.01~0.5 mass parts of carbon nanotube.The structure feature of the composite material is：Silicon rubber filling is in graphite in composite material
In the three-dimensional continuous conduction network skeleton that alkene/carbon nanotube is constructed, conducting matrix grain is interweaved by graphene and carbon nanotube
The continuous poriferous material of three-dimensional formed.The preparation method of the composite material is：First construct three-dimensional continuous graphene/carbon nanometer
Then the double conductive network skeletons of pipe backfill silicon rubber, vulcanization sizing again.It solves graphene and carbon nanotube in silicon rubber base
The problem of being difficult to form uniformly continuous conductive network and low conductive network conductivity in body, at low sizing dosage (≤1.5wt%)
Under, the high conductivity of target composite material is realized, provides not only a kind of novel electromagnetic shielding lightweight silastic material, and
And provide a kind of new method to prepare High Performance Shielding composite material based on other conductive fillers and polymeric matrix.
In order to achieve the above objectives, three-dimensional continuous graphite alkene/conductive network of carbon nanotubes skeleton of the invention, with graphite oxide
Alkene and unmodified carbon nanotube are raw material, using graphene oxide to the excellent water dispersibility of carbon nanotube, by colloidal sol-solidifying
Glue, freeze-drying and thermal reduction process are made.
Graphene oxide is stripping product of the graphite oxide by being ultrasonically treated or high-speed stirred is realized in aqueous medium.Oxygen
Graphite is prepared using Hummers methods；A concentration of 1~15mg/ml of graphite oxide；Supersound process condition is 40~500W/25
~500kHz/20~60min；High-speed stirred condition is 3000~12000rpm/30~120min.
Carbon nanotube is that single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube or above two or three kinds of carbon are received
The mixture of mitron.
Graphene/carbon nano-tube conductive network skeleton is prepared using following steps：
1) uniform and stable graphene oxide/carbon nano-tube hybridization particle moisture is made by supersound process or high-speed stirred
Dispersion liquid.A concentration of 1~10mg/ml of graphene oxide, a concentration of 0.1~10mg/ml of carbon nanotube；Supersound process condition is
40~500W/25~500kHz/1~60min；High-speed stirred condition is 500~10000rpm/1~60min.
2) chemical reducing agent is added in into graphene oxide/carbon nano-tube hybridization particle water dispersion liquid, heated reaction is made
Electronation graphene oxide/carbon nanotube hydrogel.Chemical reducing agent for hydrazine hydrate, dimethylhydrazine, phenylhydrazine, to sulfonyloxy methyl
Hydrazine, hydrogen iodide, tannic acid, pyrogallol, vitamin C, aniline, ethylenediamine, ammonium hydroxide, hydroquinone, tea polyphenols, sodium citrate, boron
One or more mixtures in sodium hydride, glucose, fructose, sucrose；The mass ratio of chemical reducing agent and graphene oxide
It is 1：1~50：1；Heating reaction condition is 50~95 DEG C/1~48h.
3) by electronation graphene oxide/carbon nanotube hydrogel freeze forming, obtained by freeze drying electronation
Graphene oxide/carbon nanotube aerogel.Freeze forming condition for -196~-5 DEG C/0.5~for 24 hours；Freeze-drying condition is -40
~-80 DEG C/1.3~13Pa/12~48h.
4) electronation graphene oxide/carbon nanotube aerogel is placed in inert atmosphere, three-dimensional is made even through heat-treating
Continuous graphene/carbon nano-tube network skeleton.Inert atmosphere is high pure nitrogen or argon gas；Thermal reduction condition for 500~1500 DEG C/
1~6h.
The present invention silicon rubber/graphene/carbon nano tube nanocomposite material be by by silicon rubber backfill into graphene/
Made from carbon nano tube network skeleton and then vulcanization sizing.Silicon rubber is heat vulcanized silicone rubber, condensed room temperature vulcanized silicon rubber
Glue or add-on type liquid silicon rubber.Preparation process is as follows：
1) silicon rubber is dissolved in low boiling point organic solvent and is configured to required silicone rubber solution.Low boiling point organic solvent is
N-hexane, acetone, chloroform, dichloromethane or tetrahydrofuran；A concentration of 5~90wt% of silicone rubber solution.
2) graphene/carbon nano-tube network skeleton is immersed into silicone rubber solution, bubble and organic molten is removed through vacuum aided
Agent backfills silicon rubber into graphene/carbon nano-tube network skeleton.
3) by silicon rubber vulcanization, target composite material is made.Vulcanization process condition is 25~200 DEG C/10min~for 24 hours.
Compared with prior art, the invention has the advantages that：(1) graphene oxide doubles as the dispersion of carbon nanotube
The raw material of auxiliary agent and composite three dimensional conductive network skeleton can not only ensure the structural homogeneity of three-dimensional network skeleton, and
And the use of additional dispersing aid is avoided, technique is simplified, reduces cost；
(2) compared with hydrothermal reduction combines thermal reduction technique, electronation and thermal reduction is selected to be combined to graphite oxide
Alkene is restored, and without complicated equipment, by simple process control, just can reduce the contraction of three-dimensional conductive network skeleton
Rate keeps its structural homogeneity, improves its conductivity；(3) graphene and carbon nanotube interweave distribution formation with double conductive mesh
The three-dimensional continuous conduction skeleton of network, without metallic conductive fillers it is ensured that the conductivity of conducting matrix grain, it is ensured that composite material
Stability and reliability；(4) by graphene and the compounding of carbon nanotube, with reference to " backfill method " composite material preparation process,
(≤1.5wt%) just can realize the high shield effectiveness of composite material under low sizing content (up to 35dB)；(5) the three of prebuild
It is uniform to tie up conductive network skeleton structure, filler utilization rate is high, can be effectively increased electromagnetic wave in the multiple anti-of composite inner
It penetrates, so as to fulfill the high shield effectiveness of electromagnetic shielding composite material.
Description of the drawings
Fig. 1 is that silicon rubber and its nanocomposite are imitated in the electromagnetic shielding of X-band in comparative example 1-2 and embodiment 1-4
Energy.
Fig. 2 is the atomic force microscopy and thickness of graphene oxide in embodiment 1/single-walled carbon nanotube hybrid particle
Test chart.
Fig. 3 is the stereoscan photograph of three-dimensional grapheme in embodiment 1/single-walled carbon nanotube conductive network skeleton.
Fig. 4 is the stereoscan photograph of silicon rubber/graphene/single-walled carbon nanotube nanocomposite in embodiment 1.
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings and by specific embodiment.It should be understood that following embodiments
It is to limit its protection domain for illustrating rather than.
Comparative example 1：
Add-on type liquid silicon rubber (is stepped into figure RTV615, matrix resin：Curing agent=10：1) it is dissolved in n-hexane preparation
Into the silicone rubber solution of a concentration of 70wt%, then the silicone rubber solution is poured into mold, vacuum aided removing bubble and molten
Silicon rubber finally under the conditions of 65 DEG C/4h is vulcanized and obtains pure silicone rubber material by agent.The conductivity of the pure silicone rubber material is 2
×10-13S/m, the electromagnet shield effect under X-band are 1.5dB (Fig. 1).
Comparative example 2：
Silicon rubber/graphene nanocomposite material, composition are that add-on type liquid silicon rubber (steps figure RTV615, matrix tree
Fat：Curing agent=10：1) 100 mass parts, 0.5 mass parts of graphene.The composite material is prepared using following steps：
1) graphite oxide is prepared using Hummers methods, then using water as medium, graphite oxide is removed by ultrasound and prepares oxygen
Graphite alkene aqueous dispersions.A concentration of 10mg/ml of graphite oxide, supersound process condition are 200W/250kHz/30min.
2) chemical reducing agent vitamin C is added in graphene oxide aqueous dispersions (5mg/ml)【Vitamin C/oxidation stone
Black alkene=10：1 (mass ratio)】, it is to be mixed homogenize after, electronation graphene oxide hydrogel is made in heated reaction.Heating
Reaction condition is 65 DEG C/10h.
3) by electronation graphene oxide hydrogel freeze forming, then obtained by freeze drying electronation aoxidizes stone
Black alkene aeroge.Freeze forming condition is -30 DEG C/12h, and freeze-drying condition is -55 DEG C/7.8Pa/24h.
4) by electronation graphite oxide aerogel in a nitrogen atmosphere, 800 DEG C of heat treatment 2h are obtained three-dimensional continuous
Graphene conductive network skeleton.
5) graphene network skeleton is immersed into silicon rubber/hexane solution (70wt%), bubble is removed under vacuum aided
Silicon rubber is made to backfill into graphene network skeleton with solvent.
6) by silicon rubber vulcanization, target composite material is made.Vulcanization process condition is 65 DEG C/4h.
The conductivity of silicon rubber/graphene nanocomposite material is 0.2S/m, and the electromagnet shield effect of X-band is 20dB
(Fig. 1).
Embodiment 1：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is add-on type liquid
Silicon rubber (steps figure RTV615, matrix resin：Curing agent=10：1) 100 mass parts, 0.5 mass parts of graphene, single
Manage (the organic institute TNSAR in Chengdu) 0.1 mass parts.The composite material is prepared using following steps：
1) graphite oxide is prepared using Hummers methods, then using water as medium, graphite oxide is removed by ultrasound and prepares oxygen
Graphite alkene aqueous dispersions.A concentration of 10mg/ml of graphite oxide, supersound process condition are 200W/250kHz/30min.
2) single-walled carbon nanotube is added in into graphene oxide aqueous dispersions, it is sonicated that uniform and stable oxidation stone is made
Black alkene/single-walled carbon nanotube hybrid particle dispersion liquid.A concentration of 5mg/ml of graphene oxide, single-walled carbon nanotube it is a concentration of
1mg/ml, supersound process condition are 200W/250kHz/30min.Fig. 2 is graphene oxide/single-walled carbon nanotube hybrid particle
Atomic force microscopy and thickness test chart.Atomic force microscope test shows the thickness of graphene oxide as 1nm, single wall carbon
The caliber of nanotube is 1.7nm, illustrates graphene oxide for individual layer, and single-walled carbon nanotube be stripped into it is single.This knot
Fruit proves that under the auxiliary of graphene oxide single-walled carbon nanotube can be realized homodisperse.
3) chemical reducing agent vitamin C is added in graphene oxide/single-walled carbon nanotube hybrid particle aqueous dispersions【Dimension
Raw element C/ graphene oxide=10：1 (mass ratio)】, it is to be mixed homogenize after, electronation graphite oxide is made in heated reaction
Alkene/single-walled carbon nanotube hydrogel.Heating reaction condition is 65 DEG C/10h.
4) by electronation graphene oxide/single-walled carbon nanotube hydrogel freeze forming, then obtained by freeze drying
Electronation graphene oxide/single-walled carbon nanotube aeroge.Freeze forming condition be -30 DEG C/12h, freeze-drying condition for -
55℃/7.8Pa/24h.Fig. 3 is the scanning electron microscopic picture of three-dimensional grapheme/single-walled carbon nanotube conductive network skeleton.From figure
As can be seen that the cell size of three-dimensional grapheme/single-walled carbon nanotube conductive network skeleton is uniform, part single-walled carbon nanotube is born
It is loaded on graphene, part single-walled carbon nanotube is overlapped between graphene, and graphene and single-walled carbon nanotube are interweaved shape
Into the three-dimensional conductive network of even structure.
5) by electronation graphene oxide/single-walled carbon nanotube aeroge in a nitrogen atmosphere, 800 DEG C of heat treatment 2h,
Obtain three-dimensional continuous graphene/single-walled carbon nanotube conductive network skeleton.
6) graphene/single-walled carbon nanotube network skeleton is immersed into silicon rubber/hexane solution (70wt%), it is auxiliary in vacuum
Help lower removing bubble and solvent that silicon rubber is made to backfill into graphene/single-walled carbon nanotube network skeleton.
7) by silicon rubber vulcanization, target composite material is made.Vulcanization process condition is 65 DEG C/4h.Fig. 4 is silicon rubber/stone
The scanning electron microscopic picture of black alkene/single-walled carbon nanotube nanocomposite.It can be seen from the figure that three-dimensional grapheme/single wall carbon
Nanotube conductive network skeleton is completely retained in the composite, and silicon rubber is uniformly filled into the abscess of conductive network.
The conductivity of silicon rubber/graphene/single-walled carbon nanotube nanocomposite be 310S/m, the electromagnetic screen of X-band
Efficiency is covered for 33dB (Fig. 1).Compared with comparative example 1 and comparative example 2, single-walled carbon nanotube can significantly improve silicon rubber nano and answer
Being used in compounding for the conductivity and electromagnet shield effect of condensation material, graphene and single-walled carbon nanotube can be under low sizing content
Assign the higher conductivity of silicon rubber nano composite material and electromagnet shield effect.
Embodiment 2：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is add-on type liquid
Silicon rubber (steps figure RTV615, matrix resin：Curing agent=10：1) 100 mass parts, 0.5 mass parts of graphene, single
Manage (the organic institute TNSAR in Chengdu) 0.1 mass parts.The composite material is prepared using step similar to Example 1, and difference is：
Ultrasound stripping graphite oxide is replaced to prepare graphene oxide aqueous dispersions using high-speed stirred in step 1).High-speed stirring
Condition is mixed as 5000rpm/60min.
Graphene oxide/single-walled carbon nanotube hybrid particle moisture is prepared in step 2) instead of ultrasound using high-speed stirred to dissipate
Liquid.High-speed stirred condition is 5000rpm/30min.
The conductivity of silicon rubber/graphene/single-walled carbon nanotube nanocomposite be 333S/m, the electromagnetic screen of X-band
Efficiency is covered for 34dB (Fig. 1).Compared with Example 1, in composition under the same conditions, ultrasound is replaced to prepare work by high-speed stirred
The composite material of similar nature can be made in skill.
Embodiment 3：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is add-on type liquid
Silicon rubber (steps figure RTV615, matrix resin：Curing agent=10：1) 100 mass parts, 0.5 mass parts of graphene, multi-wall carbon nano-tube
Manage (the organic institute TNGM2 in Chengdu) 0.1 mass parts.The composite material is prepared using step same as Example 1.
The conductivity of silicon rubber/graphene/multi-walled carbon nanotube nanocomposite be 287S/m, the electromagnetic screen of X-band
Efficiency is covered for 30dB (Fig. 1).Compared with Example 1, in terms of Electrical Conductivity of Composites and capability of electromagnetic shielding is improved, multi wall carbon
Nanotube is effective not as good as single-walled carbon nanotube.
Embodiment 4：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is condensed type room temperature
Sulphurated siliastic (the gloomy hair in Chengdu, one-component) 100 mass parts, 0.05 mass parts of graphene, single-walled carbon nanotube (the organic institute in Chengdu
TNSAR) 0.1 mass parts, multi-walled carbon nanotube (the organic institute TNGM2 in Chengdu) 0.1 mass parts.The composite material uses and embodiment
Prepared by 1 similar step, difference is：
Graphene oxide aqueous dispersions are prepared using high-speed stirred stripping graphite oxide in step 1).The concentration of graphite oxide
For 1mg/ml；High-speed stirred condition is 3000rpm/120min.
Graphene oxide/single-walled carbon nanotube hybrid particle aqueous dispersions are prepared using high-speed stirred in step 2).Oxidation
A concentration of 1mg/ml of graphene, a concentration of 2mg/ml of single-walled carbon nanotube, a concentration of 2mg/ml of multi-walled carbon nanotube are high
Fast stirring condition is 500rpm/60min.
Chemical reducing agent uses hydrazine hydrate in step 3)【Hydrazine hydrate/graphene oxide=1：1 (mass ratio)】.Heating reaction
Condition is 50 DEG C/3h.
The conductivity of silicon rubber/graphene/single-walled carbon nanotube nanocomposite be 245S/m, the electromagnetic screen of X-band
Efficiency is covered for 28dB (Fig. 1).
Embodiment 5：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is condensed type room temperature
Sulphurated siliastic (the gloomy hair in Chengdu, one-component) 100 mass parts, 1 mass parts of graphene, multi-walled carbon nanotube (the organic institute in Chengdu
TNGM2) 0.5 mass parts.The composite material is prepared using step similar to Example 1, and difference is：
A concentration of 15mg/ml of graphite oxide in step 1), supersound process condition are 500W/500kHz/60min.
A concentration of 10mg/ml of graphene oxide in step 2), a concentration of 5mg/ml of multi-walled carbon nanotube are ultrasonically treated
Condition is 500W/500kHz/60min.
Chemical reducing agent uses sodium borohydride in step 3)【Sodium borohydride/graphene oxide=5：1 (mass ratio)】.Heating
Reaction condition is 50 DEG C/48h.
Freeze forming condition is -196 DEG C of (liquid nitrogen)/0.5h in step 4), and freeze-drying condition is -40 DEG C/1.3Pa/
48h。
Heat treatment condition is under nitrogen atmosphere, 500 DEG C are heat-treated 6h in step 5).
Using the tetrahydrofuran solution of silicon rubber, a concentration of 90wt% in step 6).
In step 7) vulcanization process condition of silicon rubber for 25 DEG C/for 24 hours.
The conductivity of silicon rubber/graphene/multi-walled carbon nanotube nanocomposite be 670S/m, the electromagnetic screen of X-band
Efficiency is covered for 37dB (Fig. 1).
Embodiment 6：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is condensed type room temperature
Sulphurated siliastic (the gloomy hair in Chengdu, one-component) 100 mass parts, 0.25 mass parts of graphene, double-walled carbon nano-tube (the organic institute in Chengdu
TND) 0.5 mass parts.The composite material is prepared using step similar to Example 5, and difference is：
Graphene oxide aqueous dispersions are prepared using high-speed stirred stripping graphite oxide in step 1).High-speed stirred condition is
12000rpm/30min。
Graphene oxide/double-walled carbon nano-tube hybrid particle aqueous dispersions are prepared using high-speed stirred in step 2).Oxidation
A concentration of 5mg/ml of graphene, a concentration of 10mg/ml of double-walled carbon nano-tube, high-speed stirred condition are 10000rpm/1min.
Chemical reducing agent uses sodium citrate in step 3)【Sodium citrate/graphene oxide=5：1 (mass ratio)】.Heating
Reaction condition is 95 DEG C/1h.
The conductivity of silicon rubber/graphene/double-walled carbon nano-tube nanocomposite be 346S/m, the electromagnetic screen of X-band
Efficiency is covered for 35dB (Fig. 1).
Embodiment 7：
A kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, the three-dimensional conductive of the composite material
Network skeleton is the continuous poriferous material of three-dimensional being interweaved by graphene and carbon nanotube, and composition is thermal vulcanization silicon
Rubber (eastern rank of nobility 110-6S, vulcanizing agent are 2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane of 2wt%) 100 mass parts,
0.5 mass parts of graphene, single-walled carbon nanotube (the organic institute TNSAR in Chengdu) 0.01 mass parts.The composite material uses and implementation
Prepared by the similar step of example 1, difference is：
A concentration of 5mg/ml of graphite oxide in step 1), supersound process condition are 40W/25kHz/20min.
A concentration of 0.1mg/ml of single-walled carbon nanotube in step 2), supersound process condition are 40W/25kHz/1min.
Chemical reducing agent aniline and ethylenediamine are used in step 3)【Aniline/ethylenediamine/graphene oxide=25：25：1 (matter
Amount ratio)】.Heating reaction condition is 70 DEG C/3h.
In step 4) freeze forming condition for -5 DEG C/for 24 hours, freeze-drying condition be -80 DEG C/13Pa/12h.
Heat treatment condition is under argon gas atmosphere, 1500 DEG C are heat-treated 1h in step 5).
Using the chloroformic solution of silicon rubber, a concentration of 5wt% in step 6).
The vulcanization process condition of silicon rubber is 200 DEG C/10min in step 7).
The conductivity of silicon rubber/graphene/single-walled carbon nanotube nanocomposite be 83S/m, the electromagnetic shielding of X-band
Efficiency is 25dB (Fig. 1).
The above embodiments merely illustrate the technical concept and features of the present invention, and the protection model of the present invention can not be limited with this
It encloses.All equivalent transformations done according to spirit of the invention or modification should all be covered within the scope of the present invention.
Claims (6)
1. a kind of electromagnetic shielding silicon rubber/graphene/carbon nano tube nanocomposite material, which is characterized in that in composite material
In the three-dimensional continuous conduction network skeleton that silicon rubber filling is constructed in graphene/carbon nano-tube, conducting matrix grain be by graphene with
The continuous poriferous material of three-dimensional that carbon nanotube is interweaved, composition are：100 mass parts of silicon rubber, graphene 0.05~1
Mass parts, 0.01~0.5 mass parts of carbon nanotube.
2. silicon rubber/graphene/carbon nano tube nanocomposite material according to claim 1, which is characterized in that used
Silicon rubber is heat vulcanized silicone rubber, condensed room temperature vulcanized silicone rubber or add-on type liquid silicon rubber.
3. silicon rubber/graphene/carbon nano tube nanocomposite material according to claim 2, which is characterized in that used
Graphene is the redox graphene through electronation and thermal reduction two ranks processing.
4. silicon rubber/graphene/carbon nano tube nanocomposite material according to claim 3, which is characterized in that used
Carbon nanotube is the mixed of single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube or above two or three kinds of carbon nanotubes
Close object.
5. a kind of preparation side of claim 1-4 any one of them silicon rubber/graphene/carbon nano tube nanocomposite material
Method, which is characterized in that three-dimensional continuous graphene/carbon nano-tube conductive network skeleton is first constructed, then backfills silicon rubber again,
Vulcanization sizing.
6. the preparation method of silicon rubber/graphene/carbon nano tube nanocomposite material according to claim 5, feature
It is, including following preparation process：
(1) graphene oxide aqueous dispersions：In aqueous medium, graphite oxide is removed into oxygen by supersound process or high-speed stirred
Graphite alkene, is made graphene oxide aqueous dispersions, and graphite oxide used is prepared using improved Hummers methods；Aoxidize stone
A concentration of 1~15mg/ml of ink；Supersound process condition is 40~500W/25~500kHz/20~60min；High-speed stirred condition
For 3000~12000rpm/30~120min；
(2) graphene oxide/carbon nano-tube hybridization particle water dispersion liquid：Carbon nanotube is added in into graphene oxide aqueous dispersions,
Uniform and stable graphene oxide/carbon nano-tube hybridization particle water dispersion liquid is made in sonicated or high-speed stirred, used
A concentration of 1~10mg/ml of graphene oxide, a concentration of 0.1~10mg/ml of carbon nanotube；Supersound process condition for 40~
500W/25~500kHz/1~60min；High-speed stirred condition is 500~10000rpm/1~60min；
(3) electronation graphene oxide/carbon nanotube hydrogel：Chemical reducing agent is added in into graphene oxide/carbon nanotube
Electronation graphene oxide/carbon nanotube hydrogel is made in hybrid particle aqueous dispersions, heated reaction.Chemistry used is also
Former agent for hydrazine hydrate, dimethylhydrazine, phenylhydrazine, to sulfonyloxy methyl hydrazine, hydrogen iodide, tannic acid, pyrogallol, vitamin C, aniline, second
It is one or more in diamines, ammonium hydroxide, hydroquinone, tea polyphenols, sodium citrate, sodium borohydride, glucose, fructose, sucrose
Mixture；The mass ratio of chemical reducing agent and graphene oxide is 1：1~50：1；Heat reaction condition for 50~95 DEG C/1~
48h；
(4) electronation graphene oxide/carbon nanotube aerogel：By electronation graphene oxide/carbon nanotube hydrogel
Freeze forming, obtained by freeze drying electronation graphene oxide/carbon nanotube aerogel, freeze forming condition used
For -196~-5 DEG C/0.5~for 24 hours；Freeze-drying condition is -40~-80 DEG C/1.3~13Pa/12~48h；
(5) three-dimensional continuous graphene/carbon nano-tube network skeleton：By electronation graphene oxide/carbon nanotube aerogel
Inert atmosphere is placed in, three-dimensional continuous graphene/carbon nano-tube network skeleton is made through heat-treating, inert atmosphere used is height
Pure nitrogen gas or argon gas；Thermal reduction condition is 500~1500 DEG C/1~6h；
(6) silicon rubber/graphene/carbon nano tube nanocomposite material：Graphene/carbon nano-tube network skeleton is immersed into silicon rubber
Low boiling point organic solvent solution, remove bubble and organic solvent through vacuum aided, vulcanization sizing be made silicon rubber/graphene/
Carbon nanotube composite materials, low boiling point organic solvent used are n-hexane, acetone, chloroform, dichloromethane or tetrahydrochysene furan
It mutters；A concentration of 5~90wt% of silicone rubber solution；The vulcanization process condition of silicon rubber is 25~200 DEG C/10min~for 24 hours.
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