WO2019109726A1 - 电磁屏蔽填料、包含其的电磁屏蔽涂料及其制备方法和应用 - Google Patents

电磁屏蔽填料、包含其的电磁屏蔽涂料及其制备方法和应用 Download PDF

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WO2019109726A1
WO2019109726A1 PCT/CN2018/109844 CN2018109844W WO2019109726A1 WO 2019109726 A1 WO2019109726 A1 WO 2019109726A1 CN 2018109844 W CN2018109844 W CN 2018109844W WO 2019109726 A1 WO2019109726 A1 WO 2019109726A1
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Prior art keywords
electromagnetic shielding
filler
coating
graphene
shielding filler
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PCT/CN2018/109844
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English (en)
French (fr)
Inventor
孙琳
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中车青岛四方机车车辆股份有限公司
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Priority claimed from CN201711299089.6A external-priority patent/CN108184325B/zh
Priority claimed from CN201711296254.2A external-priority patent/CN108034313B/zh
Application filed by 中车青岛四方机车车辆股份有限公司 filed Critical 中车青岛四方机车车辆股份有限公司
Priority to US16/765,841 priority Critical patent/US11441050B2/en
Priority to SG11202003889SA priority patent/SG11202003889SA/en
Priority to JP2020519352A priority patent/JP7123132B2/ja
Priority to EP18886004.3A priority patent/EP3723465B1/en
Publication of WO2019109726A1 publication Critical patent/WO2019109726A1/zh

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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
    • H05K9/0092—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive pigments, e.g. paint, ink, tampon printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron

Definitions

  • the invention relates to an electromagnetic shielding filler, an electromagnetic shielding coating comprising the same, a preparation method and application thereof, and belongs to the technical field of functional materials.
  • the electromagnetic shielding paint absorbs, absorbs and multiple reflections of incident electromagnetic waves, so that the energy of the incident electromagnetic wave is greatly reduced, and the electromagnetic shielding effect is exerted.
  • the existing electromagnetic shielding coatings are mainly conductive coatings, and the conductive fillers are generally metal powders such as gold, silver, copper, nickel, and non-metal powders such as carbon black and graphite.
  • Gold powder and silver powder have good electrical conductivity and chemical stability, and have been applied in key electronic equipment such as spacecraft, aircraft, and ships, but they are expensive, dense, and limited in large-area use.
  • the performance of copper powder and nickel powder is similar to that of silver, but it is easy to oxidize, the conductivity is unstable, and the electromagnetic shielding coating disposed is poor in durability.
  • carbon black and graphite powder have good dispersibility and low cost, but have poor electrical conductivity.
  • CN201610989480.8 discloses a preparation method of silver-plated copper powder filler for electromagnetic shielding coating, adding ascorbic acid into copper sulfate mixed solution, reacting for at least 1 hour to obtain copper powder; then adding silver nitrate solution to EDTA, heating reaction, And reacted with copper powder to obtain silver-plated copper powder.
  • the copper powder obtained by the invention has a particle diameter of 1-10 ⁇ m, a smooth surface, little change in size after silver plating, and excellent electrical conductivity, and is suitable for electromagnetic shielding coatings, but the silver-plated copper powder obtained by the method mainly plays a conductive role. There is limited response to the low frequency magnetic field.
  • CN200910272807.X discloses a preparation method of a silver-coated glass microbead composite particle electromagnetic shielding filler.
  • the novel electromagnetic shielding filler is prepared by firstly thiolating or aminating the surface of the template by using clean glass microbeads as a template. After modification, the silver nanoparticles are continuously deposited on the surface of the template and gradually grown to obtain silver-coated glass microbead composite particles with complete core-shell structure; then the template is dissolved in hydrofluoric acid solution, and then Filtering, washing and drying to obtain a structurally intact hollow silver microsphere as an electromagnetic shielding filler.
  • the novel electromagnetic shielding filler prepared by the invention has good electrical conductivity, and the electromagnetic shielding composite material prepared by using the same as the existing conductive silver powder is at least reduced by 65% and the weight is reduced by more than 80%, and the electromagnetic shielding composite material prepared by using the same as the shielding filler has better shielding performance.
  • the electromagnetic shielding filler obtained by the method mainly plays a conductive role, has limited response to the low frequency magnetic field band, and affects the shielding application of the electromagnetic shielding coating in the magnetic field band.
  • CN201510873045.4 discloses a heat conductive conductive composite material containing graphene, a preparation method and application thereof, and uniformly mixing a thermal conductive conductive filler mixed with silver powder and graphene with an organic polymer elastic material such as vinyl silicone oil, and passing silver powder.
  • the large-size particle filler cooperates with the highly thermally conductive and conductive graphene to construct more and more transparent thermal conductive network in the organic polymer matrix, thereby obtaining an organic polymer composite material having excellent thermal conductivity, good elasticity and flexibility.
  • the composite material has a simple preparation process, a thermal conductivity of up to 12 W/mK, a conductivity of up to 500 S/m, and an electromagnetic shielding performance of up to 45 dB.
  • the electromagnetic shielding filler obtained by the method mainly exerts an electric loss effect, and has a shielding effect only on the medium and high frequency, and has limited shielding effect on the magnetic field in the middle and low frequency bands.
  • CN 201510896392.9 discloses a preparation method of electromagnetic shielding coating, which uses non-metal parts as a application object, and uses graphene and conductive carbon black as functional fillers to prepare a lightweight, long-lasting, series based on highly conductive graphene functional filler.
  • the electromagnetic shielding coating material can not only effectively improve the electromagnetic protection capability of the equipment, but also meet the requirements of lightweight equipment, but the electromagnetic shielding coating is mainly for high frequency electromagnetic shielding.
  • CN 201010561198.2 discloses a composite coating electromagnetic shielding coating and a composite coating electromagnetic shielding material prepared thereof, the composite coating electromagnetic shielding coating comprising a conductive layer coating having a reflective function and an absorbing layer coating having an absorption function.
  • the electromagnetic shielding coating uses nickel powder as a conductive filler and ordinary magnetic powder as a magnetic conductive filler, which has a high density and is easily oxidized to affect the service life of the coating.
  • CN 201611243277.2 discloses a modified graphene electromagnetic shielding coating comprising a modified graphene slurry, a resin, a pigment filler, an auxiliary agent and a solvent, the modified graphene slurry comprising a graphene using a modifier
  • the modified graphene obtained by the modification is an organic molecule having a large ⁇ bond conjugate structure, and the resin is an acrylic resin.
  • the electromagnetic shielding filler obtained by the method also plays a role mainly in electrical loss, has a shielding effect only on the medium and high frequency, and has limited shielding effect on the magnetic field in the middle and low frequency bands.
  • the present invention provides a lightweight high-efficiency electromagnetic shielding filler for a carbon fiber composite material, which uses a melamine sponge as a carrier, and attaches Fe(NO 3 ) 3 and graphene oxide to the sponge by solution immersion treatment.
  • a one-step heat treatment results in a FeOx/graphene composite electromagnetic shielding filler having a macroporous structure of a sponge, ferrite and graphene covering the surface of the pore wall; and having electrical loss and magnetic loss to exhibit superior electromagnetic shielding performance.
  • the present invention is achieved by the following technical solutions.
  • a shielding filler comprising a melamine sponge as a carrier and having a surface covered with FeOx/graphene; wherein FeOx is preferably present in the following form: one or more of Fe, FeO, Fe 2 O 3 or Fe 3 O 4 , wherein FeOx accounts for 5-99% of the total mass of the shielding filler, and graphene accounts for 1-95% of the total mass of the shielding filler.
  • the shielding filler has a porosity of 65-85%, a magnetic saturation strength of 86-95 emu/g, a coercive force of 158-210 Oe, and a response frequency band of 100 kHz to 18 GHz.
  • the invention also provides a preparation method of a shielding filler, comprising:
  • the step (1) is specifically: adding an iron salt to the aqueous dispersion of graphene oxide to control the Fe 3+ concentration to be 5 mg/ml to 500 mg/ml, preferably 10 to 200 mg/ml.
  • the concentration of the aqueous dispersion of graphene oxide is from 0.5 mg/ml to 5.0 mg/ml, preferably from 1.0 to 5.0 mg/ml, such as 2.0 mg/ml.
  • the iron salt is one or more selected from the group consisting of Fe(NO 3 ) 3 , FeCl 3 , Fe 2 (SO 4 ) 3 , and iron acetate.
  • the immersion time is from 0.5 h to 5 h, preferably from 2 to 5 h.
  • the drying temperature is from 50 ° C to 150 ° C, preferably from 80 to 110 ° C.
  • the Fe 3+ -graphene oxide / melamine sponge obtained in the step (2) is heated at a rate of 1 to 20 ° C / min to 300 ° C to 1200 ° C for heat treatment, and sieved to obtain FeOx / graphene.
  • Electromagnetic shielding filler preferably, the heating rate is 5-10 ° C / min, and the heat treatment temperature is 500-800 ° C.
  • the invention also provides for the use of the shielding filler in electromagnetic shielding materials on trains, airplanes, ships or transformers.
  • the train preferably uses a carbon fiber composite body.
  • the present invention also provides a barrier coating comprising the above-described barrier filler.
  • the invention also provides a lightweight high-efficiency graphene-based electromagnetic shielding coating for rail vehicles and a preparation method thereof, which are prepared by using a polyester resin having certain elasticity and a fluorine-modified hydroxy acrylic resin excellent in weather resistance as a base material.
  • the oxygen/graphene composite electromagnetic shielding filler and a small amount of silver fiber are used as fillers to make the coating have electrical and magnetic permeability properties, thereby improving the electromagnetic shielding performance of the coating.
  • the component A is prepared from the raw materials comprising the following parts by weight: 25-55 parts of fluorocarbon resin, 5-25 parts of elastic polyester resin, 20-30 parts of electromagnetic shielding filler, 1.5-4 parts of auxiliary agent, mixed solvent 5 ⁇ 10 copies;
  • the component B is selected from the group consisting of isocyanates.
  • the fluorocarbon resin is an ethylene polymer grafted with a fluorine atom; preferably GK570, polychlorotrifluoroethylene/vinyl ether resin FEVE. It not only has good weatherability, but also has low surface energy properties, which can give the coating good stain resistance.
  • the elastic polyester resin is an elastic polyester modified acrylic resin, and the molecular formula contains irregular, relatively large molecular weight polyols and long-chain fatty acids; preferably FTH elastic resin.
  • said relatively large molecular mass means that the relative molecular mass is greater than 2000, preferably greater than 5,000.
  • the electromagnetic shielding filler is a lightweight high efficiency electromagnetic shielding filler for carbon fiber composite materials as described above.
  • the auxiliary agent is selected from one or more of an antifoaming agent, a leveling agent, a dispersing agent or a thixotropic agent; wherein the antifoaming agent is selected from the group consisting of BYK-530A, BYK110 or Deqian 6800; and the leveling agent is selected from the group consisting of BYK-320, EFKA3777 or EFKA-2022; the thixotropic agent is selected from one or more of a polyamide wax, an organic bentonite or a fumed silica.
  • the mixed solvent is composed of xylene, ethyl acetate, and cyclohexanone in a mass ratio (2.0-5.0): (1.5-4.0): (2.5-6.0), preferably 3.5:3:3.5.
  • the invention also provides a preparation method of a shielding paint, comprising:
  • the invention also provides the use of the above-mentioned shielding paint on electronic equipment in the fields of rail vehicles, airplanes, ships or transformers.
  • the invention also provides an electronic device comprising a coating prepared by the barrier coating of any of claims 1-7.
  • the obtained electromagnetic shielding filler and the electromagnetic shielding coating have both electrical and magnetic conductive properties, and the electromagnetic shielding response frequency band is wide;
  • the obtained electromagnetic shielding filler has a porous characteristic, which can increase the multi-layer reflection effect of the electromagnetic wave
  • the obtained electromagnetic shielding coating has a low density and a compound lightweight development direction
  • the obtained electromagnetic shielding coating is convenient to construct, and can be brushed, sprayed, and rolled.
  • Figure 1 is a scanning electron micrograph of the FeOx/graphene electromagnetic shielding filler obtained in the present invention.
  • 2 is a magnetic shielding effectiveness curve of the electromagnetic shielding coating of the present invention in the range of 10 kHz to 30 MHz.
  • 3 is an electric field shielding effectiveness curve of the electromagnetic shielding coating of the present invention in the range of 10 kHz to 30 MHz.
  • Example 1 A FeOx/graphene electromagnetic shielding filler
  • This embodiment provides a FeOx/graphene electromagnetic shielding filler prepared by the following method:
  • Fe(NO 3 ) 3 was added to an aqueous dispersion of graphene oxide at a concentration of 5 mg/ml to prepare a water-dispersible solution having a Fe(NO 3 ) 3 concentration of 10 mg/ml.
  • the melamine sponge was immersed in the aqueous dispersion solution of Fe(NO 3 ) 3 -graphene oxide obtained in the above step (1) for 2 hours, taken out and dried at 110 ° C for 12 hours.
  • the dried Fe(NO 3 ) 3 -graphene oxide/melamine sponge was placed in a tube furnace, heated to 600 ° C at a heating rate of 10 ° C / min for heat treatment for 3 h, and then sieved to obtain FeOx / Graphene electromagnetic shielding filler.
  • the obtained shielding filler has a porosity of 85%, a magnetic saturation strength of 95 emu/g, a coercive force of 210 Oe, and an electromagnetic shielding response frequency band of 100 kHz to 18 GHz.
  • Example 2 A FeOx/graphene electromagnetic shielding filler
  • This embodiment provides a FeOx/graphene electromagnetic shielding filler prepared by the following method:
  • FeCl 3 was added to an aqueous dispersion of graphene oxide at a concentration of 1.0 mg/ml to prepare an aqueous dispersion solution having a FeCl 3 concentration of 100 mg/ml.
  • the melamine sponge was immersed in the aqueous dispersion solution of FeCl 3 -graphene oxide obtained in the above step (1) for 3 hours, taken out and dried at 100 ° C for 20 hours.
  • the dried FeCl 3 -graphene oxide / melamine sponge was placed in a tube furnace, heated to 500 ° C at a heating rate of 5 ° C / min for heat treatment for 4 h, and then sieved to obtain FeOx / graphene electromagnetic shielding filler.
  • the obtained shielding filler has a porosity of 65%, a magnetic saturation strength of 86 emu/g, a coercive force of 200 Oe, and an electromagnetic shielding response frequency band of 100 kHz to 18 GHz.
  • Example 3 A FeOx/graphene electromagnetic shielding filler
  • This embodiment provides a FeOx/graphene electromagnetic shielding filler prepared by the following method:
  • Fe 2 (SO 4 ) 3 was added to an aqueous dispersion of graphene oxide at a concentration of 2 mg/ml to prepare an aqueous dispersion solution having a Fe 2 (SO 4 ) 3 concentration of 200 mg/ml.
  • the melamine sponge was immersed in the aqueous dispersion solution of Fe 2 (SO 4 ) 3 -graphene oxide obtained in the above step (1) for 5 hours, taken out and dried at 80 ° C for 16 hours.
  • the dried Fe 2 (SO 4 ) 3 -graphene oxide / melamine sponge was placed in a tube furnace, heated to 800 ° C at a heating rate of 10 ° C / min, heat treated for 5 h, and then sieved to obtain FeOx. / Graphene electromagnetic shielding filler.
  • the obtained shielding filler has a porosity of 78%, a magnetic saturation strength of 88 emu/g, a coercive force of 158 Oe, and an electromagnetic shielding response frequency band of 100 kHz to 18 GHz.
  • This embodiment provides a method for preparing a shielding paint, comprising:
  • the mixed solvent was composed of 3.5 g of xylene, 3 g of ethyl acetate, and 3.5 g of cyclohexanone.
  • This embodiment provides a method for preparing a barrier coating similar to that of Embodiment 4, except that the formulation of the component A is as follows:
  • GK570 fluorocarbon resin 25g FTH elastic polyester resin 25g, 6800 additive 0.3g, BYK110 additive 0.6g, EFKA2020 additive 0.3g, EFKA3777 adjuvant 0.6g, mixed solvent 5g, electromagnetic shielding filler 20g.
  • This embodiment provides a method for preparing a barrier coating similar to that of Embodiment 4, except that the formulation of the component A is as follows:
  • GK570 fluorocarbon resin 55g FTH elastic polyester resin 5g, 6800 additive 0.6g, BYK110 additive 0.3g, EFKA2020 additive 0.6g, EFKA3777 auxiliary 0.4g, mixed solvent 8g, electromagnetic shielding filler 25g.
  • Example 4 0.05 78 10KHz-18GHz 1.8
  • Example 5 2.0 twenty one 10KHz-18GHz 1.3
  • Example 6 0.4 54 10KHz-18GHz 1.6
  • the invention provides a shielding filler, a shielding coating comprising the same, a preparation method and application thereof.
  • the shielding filler of the present invention comprises a melamine sponge as a carrier, and the surface thereof is covered with FeOx/graphene; wherein, FeOx is preferably present in the following form: one or more of Fe, FeO, Fe 2 O 3 or Fe 3 O 4 ;
  • the FeOx accounts for 5-99% of the total mass of the shielding filler, and the graphene accounts for 1-95% of the total mass of the shielding filler.
  • the shielding filler of the invention has a macroporous structure of a sponge, and ferrite and graphene cover the surface of the pore wall; and has electrical loss and magnetic loss to exhibit superior electromagnetic shielding performance.
  • the obtained electromagnetic shielding coating has both conductive and magnetic permeability characteristics, and the electromagnetic shielding response frequency band is wide; the obtained electromagnetic shielding coating has a small density and a compound lightweight development direction; the coating is convenient to construct, can be brushed, sprayed, and rolled, and has a comparative advantage. Good economic value and application prospects.

Abstract

本发明涉及一种屏蔽填料、包含其的屏蔽涂料及其制备方法和应用。所述屏蔽填料以密胺海绵为载体，其表面覆盖FeOx/石墨烯。所述屏蔽涂料由甲、乙组分按照摩尔比(-OH) 甲：(-NCO) 乙＝1:1混合而成；其中所述甲组分包括：氟碳树脂、弹性聚酯树脂、电磁屏蔽填料、助剂及混合溶剂；所述乙组分为异氰酸酯。本发明所述屏蔽填料具有海绵的大孔结构，铁氧体和石墨烯覆盖在孔壁表面；具有电损耗和磁损耗而表现出优越的电磁屏蔽性能。所得电磁屏蔽涂层兼具导电和导磁特性，电磁屏蔽响应频段宽；所得电磁屏蔽涂层密度较小，符合轻量化发展方向；该涂料施工方便，可刷涂、喷涂、辊涂。

Description

电磁屏蔽填料、包含其的电磁屏蔽涂料及其制备方法和应用
交叉引用
本申请要求2017年12月8日提交的专利名称为“一种电磁屏蔽填料及其制备方法和应用”的第201711299089.6号和2017年12月8日提交的专利名称为“一种电磁屏蔽涂料及其制备方法和应用”的第201711296254.2号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。
技术领域
本发明涉及电磁屏蔽填料、包含其的电磁屏蔽涂料及其制备方法和应用，属于功能材料技术领域。
背景技术
电磁屏蔽涂料通过对入射电磁波的反射、吸收和多重反射，使得入射电磁波能量大幅缩减，起到电磁屏蔽作用。现有电磁屏蔽涂料主要为导电涂料，所加导电性填料一般是金、银、铜、镍等金属粉末和炭黑、石墨等非金属粉末。金粉和银粉的导电性和化学稳定性好，已经在航天器、飞机、船舶等关键电子设备上得到应用，但价格昂贵，密度较大，大面积使用受到限制。铜粉和镍粉的性能与银相近，但易氧化，导电性不稳定，所配置的电磁屏蔽涂料耐久性较差。炭黑、石墨粉末作为导电填料，其分散性好，价格低廉，但导电性较差。
CN201610989480.8公开了一种电磁屏蔽涂料用镀银铜粉填料的制备方法，将抗坏血酸加入硫酸铜混合溶液中，反应至少1小时，得到铜粉；然后将硝酸银溶液加入EDTA中，加热反应，并与铜粉反应得到镀银铜粉。该发明得到的铜粉，其粒径为1-10μm，表面光滑，镀银后尺寸变化不大，导电性能优异，适用于电磁屏蔽涂料用，但该方法所得镀银铜粉主要发挥导电作用，对低频磁场波段响应有限。
CN200910272807.X公开了一种银包玻璃微珠复合粒子电磁屏蔽填料的制备方法，该新型电磁屏蔽填料的制备方法是：以干净的玻璃微珠为模 板，首先对模板表面进行巯基化或氨基化修饰，再采用化学镀银方法使银纳米粒子不断地在模板表面定向沉积并逐渐长大，得到核壳结构完整的银包玻璃微珠复合粒子；然后用氢氟酸溶液溶去模板，再经抽滤、洗涤、干燥，得到结构完整的空心银微球，其作为电磁屏蔽填料。该发明制备的新型电磁屏蔽填料导电性能良好,并且对于现有导电银粉相比成本至少降低65％，重量减轻80％以上，用其作为屏蔽填料制备的电磁屏蔽复合材料具有较好的屏蔽效能。但该方法所得电磁屏蔽填料主要发挥导电作用，对低频磁场波段响应有限，影响电磁屏蔽涂料在磁场波段的屏蔽应用。
CN201510873045.4公开了一种含石墨烯的导热导电复合材料及其制备方法和应用，将银粉末等和石墨烯混合的导热导电填料与乙烯基硅油等有机高分子弹性材料均匀混合，通过银粉末等大粒径填料与高导热导电的石墨烯协同作用，在有机高分子基体中构建更多更畅通的导热导电网络，从而获得具有优异导热导电性能、良好弹性和柔性的有机高分子复合材料。所述复合材料制备工艺简单，导热率可达12W/mK，导电率可达500S/m，电磁屏蔽性能可达45dB。但是该方法所得电磁屏蔽填料主要发挥电损耗作用，仅对中高频具有屏蔽效果，对中低频段的磁场屏蔽效能有限。
CN 201510896392.9公开了一种电磁屏蔽涂层的制备方法，以非金属部件为应用对象，采用石墨烯和导电炭黑为功能填料，制备出基于高导电石墨烯功能填料的轻质、长效、系列化电磁屏蔽涂层材料，不仅能有效提升装备的电磁防护能力，而且也能满足装备轻量化的需求，但该电磁屏蔽涂层主要针对高频电磁屏蔽。CN 201010561198.2公开了一种复合涂层电磁屏蔽涂料及其制备的复合涂层电磁屏蔽材料，所述复合涂层电磁屏蔽涂料包含具有反射功能的导电层涂料和具有吸收功能的吸波层涂料。但是该电磁屏蔽涂料以镍粉作为导电填料，以普通磁粉作为导磁填料，密度很大，而且容易氧化而影响涂层服役寿命。CN 201611243277.2公开了一种改性石墨烯电磁屏蔽涂料，其包括改性石墨烯浆料、树脂、颜填料、助剂及溶剂，所述改性石墨烯浆料包括采用改性剂对石墨烯进行改性得到的改性石墨 烯，所述改性剂为具有大π键共轭结构的有机分子，所述树脂为丙烯酸树脂。但是该方法所得电磁屏蔽填料同样主要发挥电损耗作用，仅对中高频具有屏蔽效果，对中低频段的磁场屏蔽效能有限。
发明内容
为了解决上述技术问题，本发明提出一种碳纤维复合材料用的轻质高效电磁屏蔽填料，其采用密胺海绵作为载体，通过溶液浸渍处理使海绵附着Fe(NO 3) 3与氧化石墨烯，再一步热处理得到FeOx/石墨烯复合电磁屏蔽填料，该填料具有海绵的大孔结构，铁氧体和石墨烯覆盖在孔壁表面；具有电损耗和磁损耗而表现出优越的电磁屏蔽性能。
本发明是采用如下技术方案实现的。
一种屏蔽填料，其以密胺海绵为载体，其表面覆盖FeOx/石墨烯；其中，FeOx优选以下形式存在：Fe、FeO、Fe 2O 3或Fe 3O 4等中的一种或几种，其中FeOx占屏蔽填料总质量的5-99％，石墨烯占屏蔽填料总质量的1-95％。所述屏蔽填料的孔隙率为65-85％，磁饱和强度为86-95emu/g，矫顽力为158-210Oe，响应频段为100kHz-18GHz。
本发明还提供一种屏蔽填料的制备方法，包括：
(1)制备Fe 3+-氧化石墨烯的水分散溶液；
(2)密胺海绵浸渍并吸附Fe 3+-氧化石墨烯溶液，烘干；
(3)高温处理。
步骤(1)具体为：将铁盐加入氧化石墨烯的水分散液中，控制Fe 3+浓度为5mg/ml～500mg/ml，优选10-200mg/ml。
其中，所述氧化石墨烯的水分散液的浓度为0.5mg/ml～5.0mg/ml，优选1.0-5.0mg/ml，如2.0mg/ml。
其中，所述铁盐选自Fe(NO 3) 3、FeCl 3、Fe 2(SO 4) 3、乙酸铁中的一种或几种。
步骤(2)中，所述浸渍时间为0.5h～5h，优选2-5h。
步骤(2)中，所述烘干温度为50℃～150℃，优选80-110℃。
步骤(3)中，将步骤(2)所得Fe 3+-氧化石墨烯/密胺海绵以1～20℃/min速度升温至300℃～1200℃进行热处理，研磨筛分，得到FeOx/石墨烯电磁屏蔽填料；优选升温速度为5-10℃/min，热处理温度为500-800℃。
本发明还提供所述屏蔽填料在火车、飞机、船舶或变电器上电磁屏蔽材料中的应用。所述火车优选为采用碳纤维复合材料车体。
本发明还提供一种屏蔽涂料，其含有上述屏蔽填料。
本发明还提供一种轨道车辆用轻质高效石墨烯基电磁屏蔽涂料及其制备方法，通过采用具有一定弹性的聚酯树脂及耐候性能优异的氟改性羟基丙烯酸树脂为基料，添加上述铁氧体/石墨烯复合电磁屏蔽填料和少量银纤维作为填料，使涂层具有导电和导磁特性，从而提高涂层的电磁屏蔽性能。
本发明通过以下技术方案实现的：
一种电磁屏蔽涂料，由甲、乙组分按照摩尔比(-OH) 甲：(-NCO) 乙＝1:1混合而成；
其中，甲组分由包括如下重量份的原料制得：氟碳树脂25-55份，弹性聚酯树脂5-25份，电磁屏蔽填料20-30份，助剂1.5～4份，混合溶剂5～10份；
乙组分选自异氰酸酯。
所述氟碳树脂为一种接枝氟原子的乙烯聚合物；优选为GK570、聚三氟氯乙烯/乙烯基醚树脂FEVE。其不仅具有很好的耐候性，而且具有低表面能的特性，可赋予涂层良好的耐沾污性。
所述弹性聚酯树脂为弹性聚酯改性丙烯酸树脂，其分子式中含有不规整的、相对分子质量大的多元醇及长链脂肪酸；优选为FTH弹性树脂。
优选地，所述相对分子质量大是指相对分子质量大于2000，优选大于5000。
所述电磁屏蔽填料为如上所述的碳纤维复合材料用的轻质高效电磁屏蔽填料。
所述助剂选自消泡剂、流平剂、分散剂或触变剂中的一种或多种；其 中，消泡剂选自BYK-530A、BYK110或德谦6800；流平剂选自BYK-320、EFKA3777或EFKA-2022；触变剂选自聚酰胺蜡、有机膨润土或气相二氧化硅中的一种或多种。
所述混合溶剂由二甲苯、醋酸乙酯、环己酮以质量比(2.0-5.0)：(1.5-4.0)：(2.5-6.0)组成，优选3.5:3:3.5。
本发明还提供一种屏蔽涂料的制备方法，包括：
(1)将氟碳树脂、弹性聚酯树脂、助剂加入2/3混合溶剂中混合，搅拌，缓慢加入电磁屏蔽填料，分散均匀后，研磨至细度40μm，加入剩余混合溶剂，调节体系粘度至800～1000cp，过滤，出料，得到甲组分；
(2)将甲、乙组分混合，搅拌均匀，即制得电磁屏蔽涂料。
本发明还提供上述屏蔽涂料在轨道车辆、飞机、船舶或变电器等领域中电子设备上的应用。
本发明还提供一种电子设备，含有权利要求1-7任一所述屏蔽涂料制得的涂层。
本发明所述电磁屏蔽填料以及包含所述电磁屏蔽填料的电磁屏蔽涂料具有以下优点：
(1)所得电磁屏蔽填料以及电磁屏蔽涂层兼具导电和导磁特性，电磁屏蔽响应频段宽；
(2)所得电磁屏蔽填料具有多孔特性，可增加电磁波多层反射效应；
(3)以密胺海绵为原材料，废旧资源有效利用；
(4)制备方法简单，不需要复杂工艺和昂贵设备。
(5)所得电磁屏蔽涂层密度较小，复合轻量化发展方向；
(6)所得电磁屏蔽涂层施工方便，可刷涂、喷涂、辊涂。
附图说明
图1为本发明所得FeOx/石墨烯电磁屏蔽填料的扫描电镜照片。
图2为本发明电磁屏蔽涂层在10kHz-30MHz范围内磁场屏蔽效能曲线。
图3为本发明电磁屏蔽涂层在10kHz-30MHz范围内电场屏蔽效能曲线。
图4为本发明电磁屏蔽涂层在10GHz-18GHz范围内电磁场屏蔽效能曲线。
具体实施方式
在以下的实施例中提供了本发明的示例性的实施方案。以下的实施例仅通过示例的方式给出，并用于帮助普通技术人员使用本发明。所述实施例并不能以任何方式来限制本发明的范围。
实施例1 一种FeOx/石墨烯电磁屏蔽填料
本实施例提供一种FeOx/石墨烯电磁屏蔽填料，由如下方法制得：
(1)制备Fe(NO 3) 3-氧化石墨烯的水分散溶液。
将Fe(NO 3) 3加入到浓度为5mg/ml的氧化石墨烯的水分散液中，配制Fe(NO 3) 3浓度为10mg/ml的水分散溶。
(2)密胺海绵浸渍吸附Fe(NO 3) 3-氧化石墨烯溶液。
将密胺海绵浸渍在上述步骤(1)得到的Fe(NO 3) 3-氧化石墨烯的水分散溶液中2h，取出并于110℃烘干12h。
(3)高温处理制备轻质高效FeOx/石墨烯电磁屏蔽填料。
将烘干后的Fe(NO 3) 3-氧化石墨烯/密胺海绵放入管式炉中，以10℃/min升温速度升温至600℃进行加热处理3h，然后研磨筛分，得到FeOx/石墨烯电磁屏蔽填料。
经检测，所得屏蔽填料的孔隙率为85％，磁饱和强度为95emu/g，矫顽力为210Oe，电磁屏蔽响应频段为100kHz-18GHz。
实施例2 一种FeOx/石墨烯电磁屏蔽填料
本实施例提供一种FeOx/石墨烯电磁屏蔽填料，由如下方法制得：
(1)制备FeCl 3-氧化石墨烯的水分散溶液。
将FeCl 3加入到浓度为1.0mg/ml的氧化石墨烯的水分散液中，配制FeCl 3浓度为100mg/ml的水分散溶液。
(2)密胺海绵浸渍吸附FeCl 3-氧化石墨烯溶液。
将密胺海绵浸渍在上述步骤(1)得到的FeCl 3-氧化石墨烯的水分散溶液中3h，取出并于100℃烘干20h。
(3)高温处理制备轻质高效FeOx/石墨烯电磁屏蔽填料。
将烘干后的FeCl 3-氧化石墨烯/密胺海绵放入管式炉中，以5℃/min升温速度升温至500℃进行加热处理4h，然后研磨筛分，得到FeOx/石墨烯电磁屏蔽填料。
经检测，所得屏蔽填料的孔隙率为65％，磁饱和强度为86emu/g，矫顽力为200Oe，电磁屏蔽响应频段为100kHz-18GHz。
实施例3 一种FeOx/石墨烯电磁屏蔽填料
本实施例提供一种FeOx/石墨烯电磁屏蔽填料，由如下方法制得：
(1)制备Fe 2(SO 4) 3-氧化石墨烯的水分散溶液。
将Fe 2(SO 4) 3加入到浓度为2mg/ml的氧化石墨烯的水分散液中，配制Fe 2(SO 4) 3浓度为200mg/ml的水分散溶液。
(2)密胺海绵浸渍吸附Fe 2(SO 4) 3-氧化石墨烯溶液。
将密胺海绵浸渍在上述步骤(1)得到的Fe 2(SO 4) 3-氧化石墨烯的水分散溶液中5h，取出并于80℃烘干16h。
(3)高温处理制备轻质高效FeOx/石墨烯电磁屏蔽填料。
将烘干后的Fe 2(SO 4) 3-氧化石墨烯/密胺海绵放入管式炉中，以10℃/min升温速度升温至800℃进行加热处理5h，然后研磨筛分，得到FeOx/石墨烯电磁屏蔽填料。
经检测，所得屏蔽填料的孔隙率为78％，磁饱和强度为88emu/g，矫顽力为158Oe；电磁屏蔽响应频段为100kHz-18GHz。
实施例4 一种电磁屏蔽涂料的制备
本实施例提供一种屏蔽涂料的制备方法，包括：
(1)将GK570氟碳树脂30g、FTH弹性聚酯树脂15g、德谦6800助剂0.5g、BYK110助剂0.5g、EFKA2020助剂0.5g、EFKA3777助剂0.5g加入7g混合溶 剂中混合，搅拌，缓慢加入实施例1所得电磁屏蔽填料30g，分散均匀后，研磨至细度40μm，加入剩余3g混合溶剂，调节体系粘度至800～1000cp，过滤，出料，得到甲组分；
所述混合溶剂是由二甲苯3.5g、醋酸乙酯3g、环己酮3.5g组成。
(2)将甲、乙组分(异氰酸酯N3390)按照摩尔比(-OH) 甲：(-NCO) 乙＝1:1混合，搅拌均匀，即制得电磁屏蔽涂料。
实施例5
本实施例提供一种与实施例4类似的屏蔽涂料的制备方法，区别仅在于其中甲组分的配方如下：
GK570氟碳树脂25g、FTH弹性聚酯树脂25g、6800助剂0.3g、BYK110助剂0.6g、EFKA2020助剂0.3g、EFKA3777助剂0.6g，混合溶剂5g，电磁屏蔽填料20g。
实施例6
本实施例提供一种与实施例4类似的屏蔽涂料的制备方法，区别仅在于其中甲组分的配方如下：
GK570氟碳树脂55g、FTH弹性聚酯树脂5g、6800助剂0.6g、BYK110助剂0.3g、EFKA2020助剂0.6g、EFKA3777助剂0.4g，混合溶剂8g，电磁屏蔽填料25g。
效果验证
对实施例4-6所得屏蔽涂料的性能进行检测，结果如下：
涂层 电阻率/Ω.cm 磁饱和强度/emu/g 响应频段 涂层密度/g/m 3
实施例4 0.05 78 10KHz-18GHz 1.8
实施例5 2.0 21 10KHz-18GHz 1.3
实施例6 0.4 54 10KHz-18GHz 1.6
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
工业实用性
本发明提供一种屏蔽填料、包含其的屏蔽涂料及其制备方法和应用。本发明所述屏蔽填料以密胺海绵为载体，其表面覆盖FeOx/石墨烯；其中，FeOx优选以下形式存在：Fe、FeO、Fe 2O 3或Fe 3O 4中的一种或几种；所述FeOx占屏蔽填料总质量的5-99％，石墨烯占屏蔽填料总质量的1-95％。所述屏蔽涂料由甲、乙组分按照摩尔比(-OH) 甲：(-NCO) 乙＝1:1混合而成；其中所述甲组分由包括如下重量份的原料制得：25-55份的氟碳树脂、5-25份的弹性聚酯树脂、20-30份的电磁屏蔽填料、1.5～4份的助剂及5～10份的混合溶剂；所述乙组分为异氰酸酯。本发明所述屏蔽填料具有海绵的大孔结构，铁氧体和石墨烯覆盖在孔壁表面；具有电损耗和磁损耗而表现出优越的电磁屏蔽性能。所得电磁屏蔽涂层兼具导电和导磁特性，电磁屏蔽响应频段宽；所得电磁屏蔽涂层密度较小，复合轻量化发展方向；该涂料施工方便，可刷涂、喷涂、辊涂，具有较好的经济价值和应用前景。

Claims (10)

  1. 一种屏蔽填料，其特征在于，以密胺海绵为载体，其表面覆盖FeOx/石墨烯；
    其中，所述FeOx以以下形式存在：Fe、FeO、Fe 2O 3或Fe 3O 4中的一种或几种；
    所述FeOx占屏蔽填料总质量的5-99％，所述石墨烯占屏蔽填料总质量的1-95％。
  2. 根据权利要求1所述的屏蔽填料，其特征在于，所述屏蔽填料的孔隙率为65-85％，磁饱和强度为86-95emu/g，矫顽力为158-210 Oe，响应频段为100kHz-18GHz。
  3. 一种屏蔽填料的制备方法，其特征在于，其包括：
    (1)制备Fe 3+-氧化石墨烯的水分散溶液；
    (2)密胺海绵浸渍并吸附Fe 3+-氧化石墨烯溶液，烘干；
    (3)高温处理；
    优选地，步骤(1)具体为：将铁盐加入氧化石墨烯的水分散液中，控制Fe 3+浓度为5mg/ml～500mg/ml；
    和/或，所述氧化石墨烯的水分散液的浓度为0.5mg/ml～5mg/ml，优选1.0-5.0mg/ml；
    和/或，所述铁盐选自Fe(NO 3) 3、FeCl 3、Fe 2(SO 4) 3、乙酸铁中的一种或几种；
    优选地，步骤(3)中，将步骤(2)所得Fe 3+-氧化石墨烯/密胺海绵升温至300℃～1200℃进行热处理，研磨筛分，得到FeOx/石墨烯电磁屏蔽填料；所述热处理温度优选为500-800℃；
    和/或，所述升温速度为1～20℃/min，更优选为5-10℃/min。
  4. 权利要求1或2所述屏蔽填料在火车、飞机、船舶或变电器上电磁屏蔽材料中的应用。
  5. 一种屏蔽涂料，由甲、乙组分按照摩尔比(-OH) 甲：(-NCO) 乙＝1:1 混合而成；其特征在于，所述甲组分由包括如下重量份的原料制得：25-55份的氟碳树脂、5-25份的弹性聚酯树脂、20-30份的权利要求1或2所述屏蔽填料、1.5～4份的助剂及5～10份的混合溶剂；
    所述乙组分为异氰酸酯。
  6. 根据权利要求5所述的屏蔽涂料，其特征在于，所述氟碳树脂为一种接枝氟原子的乙烯聚合物；优选为GK570、聚三氟氯乙烯/乙烯基醚树脂FEVE；
    和/或，所述弹性聚酯树脂为弹性聚酯改性丙烯酸树脂，其分子式中含有不规整的、相对分子质量大的多元醇及长链脂肪酸；优选为FTH弹性树脂。
  7. 根据权利要求5或6所述的屏蔽涂料，其特征在于，所述助剂为消泡剂、流平剂、分散剂或触变剂中的一种或多种；
    优选地，所述消泡剂选自BYK-530A、BYK110或德谦6800；
    和/或，所述流平剂选自BYK-320、EFKA3777或EFKA-2022；
    和/或，所述触变剂选自聚酰胺蜡、有机膨润土或气相二氧化硅中的一种或多种；
    和/或，所述混合溶剂由二甲苯、醋酸乙酯、环己酮以质量比(2.0-5.0)：(1.5-4.0)：(2.5-6.0)组成。
  8. 权利要求5-7中任一项所述屏蔽涂料的制备方法，其特征在于，包括：
    (1)将氟碳树脂、弹性聚酯树脂、助剂加入2/3混合溶剂中混合，搅拌，缓慢加入电磁屏蔽填料，分散均匀后，研磨至细度40μm，加入剩余混合溶剂，调节体系粘度至800～1000cp，过滤，出料，得到甲组分；
    (2)将甲、乙组分混合，搅拌均匀，即制得电磁屏蔽涂料。
  9. 权利要求5-7中任一项所述屏蔽涂料在轨道车辆、飞机、船舶或变电器领域中电子设备上的应用。
  10. 一种电子设备，其特征在于，含有权利要求5-7中任一项所述屏蔽涂料制得的涂层。
PCT/CN2018/109844 2017-12-08 2018-10-11 电磁屏蔽填料、包含其的电磁屏蔽涂料及其制备方法和应用 WO2019109726A1 (zh)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113990847A (zh) * 2021-09-30 2022-01-28 哈尔滨工业大学 抗辐照封装加固的cots器件及其制备方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020899A (zh) * 2010-11-26 2011-04-20 中国人民解放军第三军医大学 复合涂层电磁屏蔽涂料及其制备的复合涂层电磁屏蔽材料
EP2835375A1 (en) * 2013-08-09 2015-02-11 Fundació Institut Català d'Investigació Química Bis-salphen compounds and carbonaceous material composites comprising them
CN105648438A (zh) * 2016-01-20 2016-06-08 梧州三和新材料科技有限公司 一种对连续非金属带材导电化和黑化处理的方法
CN107041113A (zh) * 2017-05-04 2017-08-11 哈尔滨工业大学 一种利用石墨烯海绵和聚二甲基硅氧烷进行复合制备高导电高电磁屏蔽柔性复合材料的方法
CN108034313A (zh) * 2017-12-08 2018-05-15 中车青岛四方机车车辆股份有限公司 一种电磁屏蔽涂料及其制备方法和应用
CN108184325A (zh) * 2017-12-08 2018-06-19 中车青岛四方机车车辆股份有限公司 一种电磁屏蔽填料及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173189A (zh) * 2013-03-06 2013-06-26 西北工业大学 制备还原氧化石墨烯/四氧化三铁纳米吸波材料的方法
CN103341346B (zh) * 2013-06-26 2015-07-29 江苏省环境科学研究院 一种锰铁氧体纳米颗粒与石墨烯复合物的制备方法
CN105111913B (zh) * 2015-10-08 2017-10-10 北京理工大学 石墨烯/纳米铁氧体基水性电磁屏蔽涂料及其制备方法
CN106397825B (zh) * 2016-09-21 2019-10-25 江苏盖姆纳米材料科技有限公司 适用于高温潮湿环境的石墨烯基三维多孔电磁屏蔽材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020899A (zh) * 2010-11-26 2011-04-20 中国人民解放军第三军医大学 复合涂层电磁屏蔽涂料及其制备的复合涂层电磁屏蔽材料
EP2835375A1 (en) * 2013-08-09 2015-02-11 Fundació Institut Català d'Investigació Química Bis-salphen compounds and carbonaceous material composites comprising them
CN105648438A (zh) * 2016-01-20 2016-06-08 梧州三和新材料科技有限公司 一种对连续非金属带材导电化和黑化处理的方法
CN107041113A (zh) * 2017-05-04 2017-08-11 哈尔滨工业大学 一种利用石墨烯海绵和聚二甲基硅氧烷进行复合制备高导电高电磁屏蔽柔性复合材料的方法
CN108034313A (zh) * 2017-12-08 2018-05-15 中车青岛四方机车车辆股份有限公司 一种电磁屏蔽涂料及其制备方法和应用
CN108184325A (zh) * 2017-12-08 2018-06-19 中车青岛四方机车车辆股份有限公司 一种电磁屏蔽填料及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3723465A4

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113990847A (zh) * 2021-09-30 2022-01-28 哈尔滨工业大学 抗辐照封装加固的cots器件及其制备方法
CN113990847B (zh) * 2021-09-30 2022-11-01 哈尔滨工业大学 抗辐照封装加固的cots器件及其制备方法
CN114613564A (zh) * 2022-03-23 2022-06-10 南通成泰磁材科技有限公司 一种高磁导率铁氧体磁性材料及其制备方法
CN114613564B (zh) * 2022-03-23 2023-02-10 南通成泰磁材科技有限公司 一种高磁导率铁氧体磁性材料及其制备方法
CN117794219A (zh) * 2024-02-26 2024-03-29 深圳市绚图新材科技有限公司 一种电磁屏蔽衬垫材料的制备方法
CN117794219B (zh) * 2024-02-26 2024-05-10 深圳市绚图新材科技有限公司 一种电磁屏蔽衬垫材料的制备方法

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