CN111234777A - Wave-absorbing powder, wave-absorbing material, preparation method and application thereof - Google Patents

Wave-absorbing powder, wave-absorbing material, preparation method and application thereof Download PDF

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CN111234777A
CN111234777A CN202010135761.3A CN202010135761A CN111234777A CN 111234777 A CN111234777 A CN 111234777A CN 202010135761 A CN202010135761 A CN 202010135761A CN 111234777 A CN111234777 A CN 111234777A
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wave
absorbing
powder
absorbing material
orthosilicate
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CN111234777B (en
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朱春芳
刘丽
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Shenzhen Sifa Industry Co Ltd
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D125/00Coating 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02Homopolymers or copolymers of hydrocarbons
    • C09D125/04Homopolymers or copolymers of styrene
    • C09D125/06Polystyrene
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    • C09D125/00Coating 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02Homopolymers or copolymers of hydrocarbons
    • C09D125/04Homopolymers or copolymers of styrene
    • C09D125/08Copolymers of styrene
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    • C09DCOATING 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
    • C09D133/00Coating 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32Radiation-absorbing paints
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01QANTENNAS, i.e. RADIO AERIALS
    • H01Q17/00Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073Shielding materials
    • H05K9/0081Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083Electromagnetic 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0856Iron

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Abstract

The invention discloses wave-absorbing powder, a wave-absorbing material, a preparation method and application thereof, wherein the raw material for preparing the wave-absorbing powder comprises 0.005-0.5 part of orthosilicate compounds; 0.005-0.5 part of borate compound; 0.001-0.005 part of acid; 0.001-0.005 part of amino silane coupling agent; 0.5-15 parts of absolute ethyl alcohol; 20-80 parts of wave-absorbing raw powder; the wave-absorbing material comprises: 70-90 parts of wave absorbing powder; 5-30 parts of water-based adhesive; 0.01-1 part of curing agent; 5-90 parts of a diluent; 0.1-2 parts of an auxiliary agent; the wave-absorbing material has high density, magnetic conductivity and resistivity, and meets the requirements of civil and industrial scenes.

Description

Wave-absorbing powder, wave-absorbing material, preparation method and application thereof
Technical Field
The invention relates to wave-absorbing powder, a wave-absorbing material, a preparation method and application thereof, and belongs to the technical field of functional materials.
Background
With the development of modern technologies, the application of electronic and information technologies is rapidly developed, and with the rapid popularization of various modern electronic devices such as mobile phones, more and more information systems are used and relied on by people. The radiation of electronic equipment and the leaked electromagnetic waves threaten the health and safety of human beings; information systems are transmitted by means of digitized signals and are susceptible to errors caused by electromagnetic wave interference. In the civil aspect, the wave-absorbing material can reduce or avoid electromagnetic wave interference generated by radiation electromagnetic waves of electronic and information equipment. In military aspect, the wave-absorbing material is used in stealth technology which is a key technology of modern war. Therefore, the wave-absorbing material is widely applied to the aspects of information transmission, electronic devices, microwave protection, military and the like.
However, the existing wave-absorbing material has poor characteristics such as impedance matching and the like because the magnetic conductivity is improved and the resistance is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the first purpose of the invention is to provide the wave-absorbing powder which is coated by silicon-boron composite and has good electrical properties.
The second purpose of the invention is to provide a preparation method of the wave-absorbing powder.
The third purpose of the invention is to provide a wave-absorbing material which has high density, magnetic conductivity and resistivity.
The fourth purpose of the invention is to provide a preparation method of the wave-absorbing material,
the fifth purpose of the invention is to provide the application of the wave-absorbing material for preparing electronic components, and the electronic components have stable and excellent structure and performance.
The first purpose of the invention can be achieved by adopting the following technical scheme: the wave-absorbing powder is prepared from the following raw materials in parts by weight:
Figure BDA0002397252540000021
further, the orthosilicate ester compound comprises at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate and amyl orthosilicate;
the borate ester compound comprises at least one of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate and tripentyl borate.
Further, the acid includes at least one of citric acid, lactic acid, boric acid, and acetic acid;
the wave-absorbing raw powder comprises at least one of iron powder, carbonyl iron powder, iron-silicon-aluminum alloy powder, iron-silicon-chromium alloy powder, iron-silicon-nickel powder, iron-silicon-aluminum-nickel powder and iron-nickel-molybdenum alloy powder.
The second purpose of the invention can be achieved by adopting the following technical scheme: a preparation method of wave-absorbing powder comprises the following steps:
the preparation method of the working solution comprises the following steps: adding an orthosilicate compound and a borate compound into absolute ethyl alcohol, and uniformly mixing to obtain a borate-orthosilicate ethyl alcohol solution for later use; mixing water and acid, placing at 50-85 deg.C, adding boric acid ester-orthosilicate ester ethanol solution while stirring, and keeping the temperature for 10-60min to obtain working solution;
a coupling step: mixing aminosilane coupling agent with wave-absorbing raw powder in an atomization spraying mode, and further mixing uniformly in a ball milling or grinding mode to obtain wave-absorbing raw powder subjected to coupling treatment;
mixing: mixing the coupled wave-absorbing raw powder with the working solution, and uniformly mixing in a ball milling or grinding mode to obtain a mixture;
and (3) curing: and stirring the mixture, heating, drying and curing to obtain the wave-absorbing powder.
The third purpose of the invention can be achieved by adopting the following technical scheme: a wave-absorbing material comprises the following components in parts by weight:
Figure BDA0002397252540000031
further, the water-based adhesive is at least one of polyvinyl acetate and copolymer emulsion thereof, acrylic polymer and copolymer emulsion thereof, ethylene propylene diene monomer emulsion, styrene polymer and copolymer emulsion thereof, epoxy resin and copolymer emulsion thereof, amino resin and copolymer emulsion thereof, phenolic resin and copolymer emulsion thereof, polyamide emulsion, alkyd resin emulsion, polyurethane emulsion, organic silicon resin emulsion and sodium polyacrylate.
Further, the curing agent is at least one of 1, 3-bis (t-butylperoxyisopropyl) benzene, N' -m-phenylene bismaleimide, triallyl isocyanurate, isocyanate compounds, dicumyl peroxide, diacyl peroxide, t-alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide and dialkyl peroxyketal;
the diluent is at least one of water, dimethylformamide, alcohol solvents, ether solvents, ester solvents, ketone solvents and hydrocarbon solvents;
the auxiliary agent is at least one of polyacrylic acid leveling agent, polysiloxane leveling agent, polyacrylic acid wetting agent, polysiloxane wetting agent, mineral oil defoaming agent, organic silicon defoaming agent, mannitol, polyethylene glycol and glycerol.
The fourth purpose of the invention can be achieved by adopting the following technical scheme: a preparation method of the wave-absorbing material comprises the following steps:
the preparation method of the coating slurry comprises the following steps: mixing wave-absorbing powder, a water-based adhesive, a curing agent, a diluent and an auxiliary agent to obtain coating slurry;
post-treatment: and coating, drying and mould pressing the coating slurry to obtain the wave-absorbing material.
The fifth purpose of the invention can be achieved by adopting the following technical scheme: the wave-absorbing material is applied to preparing electronic components.
Furthermore, the electronic component comprises a wave-absorbing material and an adhesive layer, a metal layer or a heat-conducting layer attached to at least one surface of the wave-absorbing material.
The formulation design principle of the invention is as follows:
in the formula of the wave-absorbing powder, the double hydrolysis of the orthosilicate compound and the borate compound is adopted to prepare the composite sol of boric acid and silicic acid, and the composite sol can reach the molecular or atomic level and can be uniformly and completely coated on the surface of the powder. The more the coating is, the electrical performance can be improved, but the magnetic conductivity is reduced if the coating is too much, and the uniformity of the coating needs to be controlled.
The wave-absorbing material provided by the invention adopts the wave-absorbing powder, and is matched with the water-based adhesive, the curing agent, the diluent and the auxiliary agent, so that the wave-absorbing material can be further prepared, the density of the wave-absorbing material can be effectively improved, and the magnetic conductivity is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the wave-absorbing powder takes an orthosilicate compound and a borate compound as raw materials, and silicon boron is compounded to coat the wave-absorbing powder, so that the wave-absorbing powder has good electrical properties;
2. the wave-absorbing material has high density, magnetic conductivity and resistivity, and meets the requirements of civil and industrial scenes;
3. the wave-absorbing material is used for preparing electronic components, and the electronic components are stable and excellent in structure and performance.
Detailed Description
The invention will be further described with reference to specific embodiments:
1. preparing wave-absorbing powder:
preparing raw materials for preparing the wave-absorbing powder according to the following parts by weight:
Figure BDA0002397252540000051
Figure BDA0002397252540000061
the preparation method of the wave-absorbing powder comprises the following steps:
the preparation method of the working solution comprises the following steps: adding an orthosilicate compound and a borate compound into absolute ethyl alcohol, and uniformly mixing to obtain a borate-orthosilicate ethyl alcohol solution for later use; mixing water and acid, placing at 70 deg.C, adding boric acid ester-orthosilicate ester ethanol solution while stirring, and keeping the temperature for 50min to obtain working solution;
a coupling step: mixing aminosilane coupling agent with wave-absorbing raw powder in an atomization spraying mode, and further mixing uniformly in a ball milling or grinding mode to obtain wave-absorbing raw powder subjected to coupling treatment;
mixing: mixing the coupled wave-absorbing raw powder with the working solution, and uniformly mixing in a ball milling or grinding mode to obtain a mixture;
and (3) curing: and stirring the mixture, heating, drying and curing to obtain the wave-absorbing powder.
Wherein the orthosilicate compound comprises at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate and amyl orthosilicate;
the borate ester compound comprises at least one of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate and tripentyl borate;
the acid comprises at least one of citric acid, lactic acid, boric acid and acetic acid;
the wave-absorbing raw powder comprises at least one of iron powder, carbonyl iron powder, iron-silicon-aluminum alloy powder, iron-silicon-chromium alloy powder, iron-silicon-nickel powder, iron-silicon-aluminum-nickel powder and iron-nickel-molybdenum alloy powder.
2. Preparing a wave-absorbing material from wave-absorbing powder:
preparing the following materials in parts by weight:
Figure BDA0002397252540000062
Figure BDA0002397252540000071
wherein the water-based adhesive is at least one of polyvinyl acetate and copolymer emulsion thereof, acrylic polymer and copolymer emulsion thereof, ethylene propylene diene monomer emulsion, styrene polymer and copolymer emulsion thereof, epoxy resin and copolymer emulsion thereof, amino resin and copolymer emulsion thereof, phenolic resin and copolymer emulsion thereof, polyamide emulsion, alkyd resin emulsion, polyurethane emulsion, organic silicon resin emulsion and sodium polyacrylate;
the curing agent is at least one of 1, 3-bis (tert-butylperoxyisopropyl) benzene, N' -m-phenylene bismaleimide, triallyl isocyanurate, isocyanate compounds, dicumyl peroxide, diacyl peroxide, tert-alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide and dialkyl peroxyketal;
the diluent is at least one of water, dimethylformamide, alcohol solvents, ether solvents, ester solvents, ketone solvents and hydrocarbon solvents;
the auxiliary agent is at least one of polyacrylic acid leveling agent, polysiloxane leveling agent, polyacrylic acid wetting agent, polysiloxane wetting agent, mineral oil defoaming agent, organic silicon defoaming agent, mannitol, polyethylene glycol and glycerol;
the selection of the wave-absorbing raw powder mainly improves the density of the wave-absorbing powder and the prepared wave-absorbing material, and the higher the density is, the closer the density is to the density of the metal iron plate, the higher the magnetic conductivity is; when the wave-absorbing material is prepared, a certain amount of resin is required to be added, and the low density of about 1.0g/cm is mainly selected3The resin can reduce the density of the wave-absorbing material and reduce the magnetic permeability, so the dosage of the two materials needs to be balanced.
The preparation method of the wave-absorbing material comprises the following steps:
the preparation method of the coating slurry comprises the following steps: mixing wave-absorbing powder, a water-based adhesive, a curing agent, a diluent and an auxiliary agent to obtain coating slurry;
post-treatment: and coating, drying and mould pressing the coating slurry to obtain the wave-absorbing material.
3. The wave-absorbing material is used for preparing electronic components: the electronic component comprises a wave-absorbing material and an adhesive layer, a metal layer or a heat-conducting layer attached to at least one surface of the wave-absorbing material.
The wave-absorbing raw powder, the water-based adhesive and the curing agent are provided by Asahi Goma (Guangzhou) synthetic materials science and technology Limited.
Example 1:
in the embodiment 1, the raw materials of the wave-absorbing powder and the components of the wave-absorbing material are shown in table 1, and the preparation process is the same as the specific embodiment;
table 1 example 1 raw materials and components of wave-absorbing material of wave-absorbing powder
Figure BDA0002397252540000081
Figure BDA0002397252540000091
Example 2:
in the embodiment 2, the raw materials of the wave-absorbing powder and the components of the wave-absorbing material are as shown in the table 2, and the preparation process is the same as the specific embodiment;
table 2 example 2 raw materials for wave-absorbing powder and components of wave-absorbing material
Figure BDA0002397252540000092
Example 3:
in the embodiment 3, the raw materials of the wave-absorbing powder and the components of the wave-absorbing material are as shown in the table 3, and the preparation process is the same as the specific embodiment;
table 3 example 3 raw materials for wave-absorbing powder and components of wave-absorbing material
Figure BDA0002397252540000101
Example 4:
in example 4, the raw materials of the wave-absorbing powder and the components of the wave-absorbing material are as shown in table 4, and the preparation process is the same as the specific embodiment;
table 4 example 4 raw materials for wave-absorbing powder and components of wave-absorbing material
Figure BDA0002397252540000102
Figure BDA0002397252540000111
Example 5:
in example 5, the raw materials of the wave-absorbing powder and the components of the wave-absorbing material are as shown in table 5, and the preparation process is the same as the specific embodiment;
table 5 example 5 raw materials for wave-absorbing powder and components of wave-absorbing material
Figure BDA0002397252540000112
Figure BDA0002397252540000121
The wave-absorbing materials obtained in examples 1-5 were tested:
and (3) magnetic permeability test: using a spectrum analyzer; and (3) surface resistance testing: using a surface resistivity tester; density: a density balance was used.
The measuring method of the suction force comprises the following steps: fixing the wave-absorbing material on a glass plate with the thickness of 20cm, wherein the thickness of the coating is 0.15mm, adopting a rubber magnetic sheet with the thickness of 100mm multiplied by 0.5mm, carrying out single-side multi-pole magnetization on the permanent magnetic material by using a magnetizing machine with the magnetic moment of 1.0mm, and the surface magnetism of the rubber magnet after the magnetization is 100 Gs. And adsorbing the magnetized rubber magnet on glass fixed with a wave-absorbing material, and detecting the vertical tension of the glass by using a tension meter to obtain vertical tension data.
The results are shown in table 6:
table 6 detection data of wave-absorbing materials of examples 1-5
Figure BDA0002397252540000122
Various other changes and modifications to the above-described embodiments and concepts will become apparent to those skilled in the art from the above description, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.

Claims (10)

1. The wave-absorbing powder is characterized in that raw materials for preparing the wave-absorbing powder comprise the following components in parts by weight:
Figure FDA0002397252530000011
2. the wave-absorbing powder of claim 1, wherein the orthosilicate compounds comprise at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate and amyl orthosilicate;
the borate ester compound comprises at least one of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate and tripentyl borate.
3. The wave-absorbing powder of claim 1 wherein the acid comprises at least one of citric acid, lactic acid, boric acid, and acetic acid;
the wave-absorbing raw powder comprises at least one of iron powder, carbonyl iron powder, iron-silicon-aluminum alloy powder, iron-silicon-chromium alloy powder, iron-silicon-nickel powder, iron-silicon-aluminum-nickel powder and iron-nickel-molybdenum alloy powder.
4. A method for preparing the wave-absorbing powder of claim 1, comprising:
the preparation method of the working solution comprises the following steps: adding an orthosilicate compound and a borate compound into absolute ethyl alcohol, and uniformly mixing to obtain a borate-orthosilicate ethyl alcohol solution for later use; mixing water and acid, placing at 50-85 deg.C, adding boric acid ester-orthosilicate ester ethanol solution while stirring, and keeping the temperature for 10-60min to obtain working solution;
a coupling step: mixing aminosilane coupling agent with wave-absorbing raw powder in an atomization spraying mode, and further mixing uniformly in a ball milling or grinding mode to obtain wave-absorbing raw powder subjected to coupling treatment;
mixing: mixing the coupled wave-absorbing raw powder with the working solution, and uniformly mixing in a ball milling or grinding mode to obtain a mixture;
and (3) curing: and stirring the mixture, heating, drying and curing to obtain the wave-absorbing powder.
5. The wave-absorbing material is characterized by comprising the following components in parts by weight:
Figure FDA0002397252530000021
6. the wave absorbing material of claim 5, wherein the water-based binder is at least one of polyvinyl acetate and its copolymer emulsion, acrylic polymer and its copolymer emulsion, ethylene propylene diene monomer emulsion, styrene polymer and its copolymer emulsion, epoxy resin and its copolymer emulsion, amino resin and its copolymer emulsion, phenolic resin and its copolymer emulsion, polyamide emulsion, alkyd resin emulsion, polyurethane emulsion, silicone resin emulsion, and sodium polyacrylate.
7. The wave absorbing material of claim 5 wherein the curing agent is at least one of 1, 3-bis (t-butylperoxyisopropyl) benzene, N' -m-phenylene bismaleimide, triallyl isocyanurate, isocyanate compounds, dicumyl peroxide, diacyl peroxide, t-alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide, and dialkyl peroxyketal;
the diluent is at least one of water, dimethylformamide, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent and a hydrocarbon solvent;
the auxiliary agent is at least one of polyacrylic acid leveling agent, polysiloxane leveling agent, polyacrylic acid wetting agent, polysiloxane wetting agent, mineral oil defoaming agent, organic silicon defoaming agent, mannitol, polyethylene glycol and glycerol.
8. A method for preparing a wave-absorbing material according to claim 5, comprising:
the preparation method of the coating slurry comprises the following steps: mixing wave-absorbing powder, a water-based adhesive, a curing agent, a diluent and an auxiliary agent to obtain coating slurry;
post-treatment: and coating, drying and mould pressing the coating slurry to obtain the wave-absorbing material.
9. Use of a wave-absorbing material according to claim 5 for the preparation of electronic components.
10. The use of the absorbing material of claim 9, wherein the electronic component comprises a absorbing material and an adhesive layer, a metal layer or a heat conducting layer attached to at least one side of the absorbing material.
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Cited By (4)

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CN111875949A (en) * 2020-08-04 2020-11-03 苏州安洁新材料有限公司 Preparation method of high-temperature-resistant hydrolysis-resistant wave-absorbing magnetic sheet
CN113321885A (en) * 2021-05-31 2021-08-31 广东海粤新材料有限公司 Preparation method of wave-absorbing material with corrosion resistance
CN113717690A (en) * 2021-10-18 2021-11-30 南京邮电大学 High-heat-conductivity composite wave-absorbing material applied to radar C wave band and preparation method thereof
CN115029064A (en) * 2022-04-14 2022-09-09 烟台万华新材料技术有限公司 Thin wave-absorbing basalt flake water-based silicone coating and preparation method thereof

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