WO2018177177A1 - 吸波材料的制备方法和吸波涂料 - Google Patents

吸波材料的制备方法和吸波涂料 Download PDF

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WO2018177177A1
WO2018177177A1 PCT/CN2018/079826 CN2018079826W WO2018177177A1 WO 2018177177 A1 WO2018177177 A1 WO 2018177177A1 CN 2018079826 W CN2018079826 W CN 2018079826W WO 2018177177 A1 WO2018177177 A1 WO 2018177177A1
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powder
reaction
absorbing material
absorbing
pickling
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PCT/CN2018/079826
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English (en)
French (fr)
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刘若鹏
赵治亚
付立顺
谢镇坤
隋爱国
魏祥
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深圳光启高等理工研究院
深圳光启尖端技术有限责任公司
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Publication of WO2018177177A1 publication Critical patent/WO2018177177A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/32—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
    • C09D123/34—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
    • 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
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • 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

Definitions

  • the invention relates to the field of material technology, in particular to a method for preparing an absorbing material and a absorbing coating.
  • Absorbing materials have a wide range of uses in military and civilian applications.
  • the principle of radar detecting an object is to emit electromagnetic waves to illuminate the target and receive echoes, and obtain signals such as the distance, azimuth and height of the object according to the echo.
  • the absorbing coating can cover the surface of the object, thereby attenuating the electromagnetic wave, converting the energy of the electromagnetic wave into other energy dissipation, or causing the electromagnetic wave to disappear due to interference.
  • the absorbing coating can effectively reduce the echo intensity of the object, thereby reducing the radar cross section and achieving the stealth effect.
  • the main method for preparing absorbing materials is the ball milling method.
  • the absorbing material prepared by this method has poor uniformity in shape and size and has a relatively discrete size distribution.
  • the drawback of this method is that it is impossible to prepare a absorbing material having a microscopic shape and uniform size, thereby further optimizing the material properties.
  • an object of the present invention is to provide a method for preparing an absorbing material and a absorbing coating, wherein liquid phase synthesis and hydrothermal reduction are combined to form a sheet absorbing material, thereby improving the purity and improvement of the absorbing material.
  • the shape and size uniformity of the absorbing material is to provide a method for preparing an absorbing material and a absorbing coating, wherein liquid phase synthesis and hydrothermal reduction are combined to form a sheet absorbing material, thereby improving the purity and improvement of the absorbing material.
  • a method for preparing a absorbing material comprising: forming a mixed solution including a reaction raw material; performing a liquid phase synthesis reaction on the mixed solution; and performing pickling and removing impurities after the reaction product; Washing and drying after pickling and removing impurities to obtain a first powder; and subjecting the first powder to a hydrothermal reduction reaction to obtain a second powder, wherein the first powder and the particles of the second powder Both are in the form of flakes, and the second powder is the absorbing material.
  • the first powder is iron oxide powder
  • the reaction raw material comprises Fe(NO3)3•9H2O, Ba(NO3)2, NaOH.
  • the mass ratio of Fe(NO3)3•9H2O, Ba(NO3)2 and NaOH is: 1 ⁇ 10:0.05 ⁇ 0.5:0.5 ⁇ 5.
  • the solvent of the mixed solution comprises water and polyethylene glycol in a volume ratio of 5:1 to 1:1, wherein the polyethylene glycol has a molecular weight of 400 to 1000.
  • the reaction product comprises a mixture of ferric oxide and BaCO3, and in the step of pickling and removing the reaction product after the reaction, BaCO3 is removed by pickling and the ferric oxide is retained.
  • the pickling uses hydrochloric acid at a concentration of 0.5 to 5 mol/L, and the immersion time is 10 to 30 hours.
  • the second powder is iron powder.
  • the step of performing the liquid phase synthesis reaction on the mixed solution comprises: stirring the mixed solution for 20 minutes to 1 hour and then placing it in a hydrothermal reaction kettle; and the hydrothermal reaction kettle is at 160 ° C ⁇ After heating at 220 ° C for 10 to 50 hours, the temperature was lowered to room temperature and the reaction product was taken out.
  • the step of performing the hydrothermal reduction reaction on the first powder comprises: placing the first powder into a tube furnace, and heating in a hydrogen gas at a temperature of 350 ° C to 900 ° C for 0.5 h to 10 h. .
  • the method further comprises: performing weak acid etching to reduce the size of the second powder.
  • the weak acid comprises at least one selected from the group consisting of hydrofluoric acid and oxalic acid.
  • the weak acid corrosion reduces at least one of a thickness and a side length of the particle pieces of the second powder.
  • a absorbing coating comprising: a film forming material; and an absorbent; wherein the absorbent is an absorbing material prepared by the above method.
  • the film forming material is a resin.
  • the absorbing material is a sheet of ferric oxide powder or iron powder.
  • the first powder material can be formed by a liquid phase synthesis reaction, and the particle shape of the first powder material is a sheet shape and has a uniform side length and thickness.
  • a difficulty in the liquid phase synthesis reaction is that the reaction product is a mixture, and thus the purity of the first powder is not good.
  • the method of the present invention employs pickling to remove unwanted solid impurities from the reaction product, thereby increasing the purity of the first powder material.
  • the first powder material is converted into a second powder material by a hydrothermal reduction reaction, and the particle shape of the second powder material is still in the form of a sheet and has a uniform side length and thickness.
  • the absorbing material prepared by the method has a uniform shape and size, and high purity, thereby improving electromagnetic absorption performance.
  • weak acid etching is employed to reduce the size of the powder particles to further enhance electromagnetic absorption properties.
  • a absorbing coating according to an embodiment of the present invention wherein an absorbing material is used as the absorbent.
  • the absorbing coating formed using the absorbing material can attain high reflection loss, and the position of the absorption band can be adjusted by adjusting the side length, thickness, coating thickness, and the like of the powder particles.
  • FIG. 1 is a flow chart of a method of preparing a absorbing material in accordance with an embodiment of the present invention.
  • 3a and 3b are scanning electron micrographs of flaky ferric oxide prepared by a method according to an embodiment of the present invention.
  • Figure 5 is a scanning electron micrograph of a flake iron powder prepared by a method in accordance with an embodiment of the present invention.
  • Figure 6 is a graph showing the frequency reflection loss of flake iron powder prepared by a method according to an embodiment of the present invention.
  • the method comprises forming a flake iron oxide powder by a liquid phase synthesis method, and forming a flake iron powder by a hydrothermal reduction method.
  • a method of forming a flaky iron oxide powder is described in the following steps S01 to S04.
  • a mixed solution including a reaction raw material is formed. For example, mix water with polyethylene glycol (molecular weight 400 ⁇ 1000) in a certain volume ratio (5:1 ⁇ 1:1) (the total volume of the solution is 40 mL), then add 1 ⁇ 10 to the mixed solution.
  • g Fe(NO3)3•9H2O, 0.05 ⁇ 0.5 g Ba(NO3)2 and 0.5 ⁇ 5 g NaOH the solution was stirred for 20 min to 1 h to form a mixed solution.
  • step S02 the mixed solution is subjected to a liquid phase synthesis reaction.
  • the mixed solution is placed in a hydrothermal reaction vessel, heated at 160 to 220 ° C for 10 to 50 hours, then cooled to room temperature, and the reaction product is taken out.
  • step S03 the reaction product after the reaction is subjected to pickling and impurity removal. For example, put it in a concentration of 0.5 ⁇ 5 In the mol/L hydrochloric acid for 10 ⁇ 30 h, the impurity BaCO3 in the product is removed.
  • step S04 washing and drying are performed after pickling and removing impurities.
  • the reaction product is washed with water and ethanol, centrifuged, and dried to obtain a sheet of ferric oxide.
  • step S03 is an XRD pattern of a reaction product containing flake iron oxide before and after pickling, wherein curves a and b respectively show XRD patterns of reaction products before and after step S03 (ie, pickling).
  • the reaction product Prior to step S03, the reaction product is a mixture of Fe2O3 and BaCO3. After step S03, BaCO3 was removed from the reaction product, leaving only Fe2O3. Thus, pickling increases the purity of Fe2O3.
  • 3a and 3b are scanning electron micrographs of flaky ferric oxide prepared by a method according to an embodiment of the invention, wherein the magnification of Fig. 3b is greater than that of Fig. 3a.
  • the sheet-formed ferric oxide formed by the method has a hexagonal shape with a side length of about 5 ⁇ m and a thickness of about 500 nm to 1000 nm.
  • step S05 is further performed to form a flaky iron powder.
  • step S05 the first powder is subjected to a hydrothermal reduction reaction to obtain flake iron powder.
  • the flake-shaped ferric oxide powder obtained by the liquid phase synthesis is placed in a tube furnace, heated at a temperature of 350 ° C to 900 ° C for 0.5 to 10 h in a hydrogen atmosphere, and then the reactant is taken out.
  • the reactant is a flake iron powder.
  • reaction product 4 is an XRD pattern of a flake iron powder prepared by a method according to an embodiment of the present invention. After the step S05, the reaction product is Fe.
  • Figure 5 is a scanning electron micrograph of a flake iron powder prepared by a method in accordance with an embodiment of the present invention.
  • the flake iron powder obtained by the hydrothermal reduction substantially maintains the shape and size of the flake-shaped ferric oxide, and the flake iron powder has a hexagonal shape and a side length of about 5 ⁇ m.
  • the thickness of the flake iron powder is about 500nm ⁇ 1000. Nm.
  • step S06 weak acid etching is performed to reduce the size of the flake iron powder.
  • the size of the flake iron powder can be changed by placing the flake iron powder in a weak acid solution having a certain concentration of hydrofluoric acid or oxalic acid. Increasing the concentration of the weak acid solution or increasing the time of the weak acid etching can make the size of the flake iron powder smaller and smaller.
  • the side length of the flake iron powder can be adjusted between 500 nm and 5 ⁇ m, and the thickness can be adjusted between 50 nm and 1000 nm.
  • Figure 6 is a graph showing the frequency reflection loss of flake iron powder prepared by a method according to an embodiment of the present invention.
  • the absorbing coating was prepared using the above-mentioned flake iron powder, and then the reflection loss at different frequencies was measured.
  • the absorption peak position of the absorbing coating corresponds to the effective absorption band and is affected by the thickness of the coating and the size of the flaky iron powder.
  • the reflection loss can reach -15 dB when the thickness of the absorbing coating is 1.1 mm. Its effective absorption band is located at ( ⁇ -10 dB) at 12 ⁇ 17 GHz. When the thickness of the absorbing coating increases, the position of the absorbing peak moves toward the low frequency direction. When the thickness of the absorbing coating is 0.9 ⁇ 3 When between mm, the reflection loss less than -10 dB can be 3.6 ⁇ 18 Observed in the range of GHz.
  • the position of the absorption peak can be adjusted by changing the size of the flake iron powder.
  • the position of the absorption peak of the absorbing coating layer at the same iron powder mass fraction moves toward the high frequency direction.
  • an absorbing coating includes at least a film-forming substance and an absorbent, and may further include an additive and a solvent, wherein the film-forming substance is, for example, a resin, and the absorbent is, for example, a flake iron powder.
  • the film-forming substance is epoxy resin, polyurethane, chlorosulfonated polyethylene or the like.
  • the absorbent is, for example, a ferrite, a metal powder, a polycrystalline/amorphous fiber or the like.
  • the absorbing coating utilizes a sheet absorbing material as an absorbent, and the shape anisotropy of the two-dimensional structure of the sheet absorbing material can break through the Snoek limit and have a high magnetic permeability in the GHz band, thereby obtaining Excellent electromagnetic wave absorption performance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
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  • Compounds Of Iron (AREA)
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Abstract

一种吸波材料的制备方法及一种吸波涂料，该制备方法包括步骤：形成包括反应原料的混合溶液；将混合溶液进行液相合成反应；将反应后的反应产物进行酸洗除杂；在酸洗除杂之后进行清洗干燥，以获得第一粉末；将第一粉末进行氢热还原反应，以获得第二粉末，第一粉末和第二粉末的颗粒均为片状，第二粉末为吸波材料。该方法可以提高吸波材料的纯度以及改善吸波材料的形状和尺寸均一性。

Description

吸波材料的制备方法和吸波涂料 技术领域
本发明涉及材料技术领域，特别是吸波材料的制备方法和吸波涂料。
 背景技术
吸波材料在军事和民用领域有着广泛的用途。雷达探测物体的原理是发射电磁波对目标进行照射并接收回波，根据回波获得物体的距离、方位和高度等信号。吸波涂层可以覆盖在物体表面上，从而衰减电磁波，将电磁波的能量转化为其他能量耗散，或者使得电磁波因干涉而消失。吸波涂料可以有效地降低物体的回波强度，从而减小雷达散射截面，实现隐身效果。
 技术问题
目前，用于制备吸波材料的主要方法为球磨法。然而，这种方法所制备出的吸波材料的形状和尺寸均一性较差，具有比较离散的尺寸分布。该方法的缺陷是不能制备出微观上形状和尺寸均一的吸波材料，进而限制了材料性能的进一步优化。
因此，期望进一步改进吸波材料的制备方法以改善形状和尺寸均一性，从而提高电磁吸收性能。
 技术解决方案
有鉴于此，本发明的目的在于提供吸波材料的制备方法和吸波涂料，其中将液相合成和氢热还原相结合以形成片状吸波材料，从而可以提高吸波材料的纯度以及改善吸波材料的形状和尺寸均一性。
根据本发明的一方面，提供一种吸波材料的制备方法，包括：形成包括反应原料的混合溶液；将所述混合溶液进行液相合成反应；将反应后的反应产物进行酸洗除杂；在酸洗除杂之后进行清洗干燥，以获得第一粉末；以及将所述第一粉末进行氢热还原反应，以获得第二粉末，其中，所述第一粉末和所述第二粉末的颗粒均为片状，所述第二粉末为所述吸波材料。
优选地，所述第一粉末为三氧化二铁粉末，所述反应原料包括Fe(NO3)3•9H2O、Ba(NO3)2、NaOH。
优选地，Fe(NO3)3•9H2O、Ba(NO3)2、NaOH的质量配比为：1~10∶0.05~0.5∶0.5~5。
优选地，所述混合溶液的溶剂包括体积比为5∶1~1∶1的水和聚乙二醇，其中，聚乙二醇的分子量为400~1000。
优选地，所述反应产物包括三氧化二铁和BaCO3的混合物，在所述将反应后的反应产物进行酸洗除杂的步骤中，通过酸洗除去BaCO3且保留三氧化二铁。
优选地，所述酸洗采用浓度为0.5~5 mol/L的盐酸，浸入时长为10~30h。
优选地，所述第二粉末为铁粉。
优选地，所述将所述混合溶液进行液相合成反应的步骤包括：将所述混合溶液搅拌20分钟至1小时后放入水热反应釜中；将所述水热反应釜在160℃~220℃温度下加热10~50h后，降至室温并取出所述反应产物。
优选地，所述将所述第一粉末进行氢热还原反应的步骤包括：将所述第一粉末放入管式炉中，并在氢气中以350℃~900℃的温度加热0.5h~10h。
优选地，在将所述第一粉末进行氢热还原反应之后，所述方法还包括：进行弱酸腐蚀，以减小所述第二粉末的尺寸。
优选地，所述弱酸包括选自氢氟酸和草酸中的至少一种。
优选地，所述弱酸腐蚀使得所述第二粉末的颗粒片的厚度和边长中的至少一个减小。
根据本发明的另一方面，提供一种吸波涂料，包括：成膜物质；以及吸收剂；其中，所述吸收剂为上述方法制备的吸波材料。
优选地，所述成膜物质为树脂。
优选地，所述吸波材料为片状的三氧化二铁粉末或铁粉末。
根据本发明实施例的方法，采用液相合成反应可以形成第一粉末材料，第一粉末材料的颗粒形状为片状，并且具有均匀的边长和厚度。液相合成反应的困难在于反应产物为混合物，因而第一粉末的纯度不佳。本发明的方法采用酸洗，从反应产物中去除不需要的固体杂质，从而提高了第一粉末材料的纯度。然后，采用氢热还原反应，将第一粉末材料转换成第二粉末材料，第二粉末材料的颗粒形状仍然为片状，并且具有均匀的边长和厚度。该方法制备的吸波材料具有均匀的形状和尺寸，以及高纯度，从而可以提高电磁吸收性能。
在进一步优选的实施例中，采用弱酸腐蚀减小粉末颗粒的尺寸，以进一步提高电磁吸收性能。
 有益效果
根据本发明实施例的吸波涂料，其中采用吸波材料作为吸收剂。采用该吸波材料形成的吸波涂层可以获得高反射损耗，并且可以通过调节粉末颗粒的边长、厚度、涂层厚度等调节吸收带的位置。
 附图说明
通过以下参照附图对本发明实施例的描述，本发明的上述以及其他目的、特征和优点将更为清楚，在附图中：
图1为根据本发明实施例的吸波材料制备方法的流程图。
图2为在酸洗前后包含片状三氧化铁的反应产物的XRD图谱；
图3a和图3b为根据本发明实施例的方法制备的片状三氧化二铁的扫描电镜照片；
图4为根据本发明实施例的方法制备的片状铁粉的XRD图谱；
图5为根据本发明实施例的方法制备的片状铁粉的扫描电镜照片。
图6为根据本发明实施例的方法制备的片状铁粉的频率反射损耗关系曲线。
 本发明的实施方式
以下将参照附图更详细地描述本发明的各种实施例。在各个附图中，相同的元件采用相同或类似的附图标记来表示。为了清楚起见，附图中的各个部分没有按比例绘制。
图1为根据本发明实施例的吸波材料制备方法的流程图。该方法包括采用液相合成法形成片状三氧化二铁粉，以及采用氢热还原法形成片状铁粉。
以下的步骤S01至S04中描述了形成片状三氧化二铁粉的方法。
在步骤S01中，形成包括反应原料的混合溶液。例如，将水与聚乙二醇（分子量400~1000）以一定的体积比（5∶1~1∶1）混合均匀（溶液总体积为40 mL），然后向该混合溶液中加入1~10 g Fe(NO3)3•9H2O、0.05~0.5 g Ba(NO3)2和0.5~5 g NaOH，将溶液搅拌20min~1 h，从而形成混合溶液。
在步骤S02中，将所述混合溶液进行液相合成反应。例如，将混合溶液放入水热反应釜中，在160~220℃温度下加热10~50 h，然后降至室温，取出反应产物。
在步骤S03中，将反应后的反应产物进行酸洗除杂。例如，将其放入浓度为0.5~5 mol/L的盐酸中10~30 h，除去产物中的杂质BaCO3。
在步骤S04中，在酸洗除杂之后进行清洗干燥。例如，将反应产物用水和乙醇洗涤、离心、干燥后，即得片状三氧化二铁。
图2为在酸洗前后包含片状三氧化铁的反应产物的XRD图谱，其中曲线a和b分别示出在步骤S03（即酸洗）之前和之后的反应产物的XRD图谱。在步骤S03之前，反应产物为Fe2O3和BaCO3的混合物。在步骤S03之后，反应产物中去除了BaCO3，仅保留Fe2O3。因而，酸洗提高Fe2O3的纯度。
图3a和图3b为根据本发明实施例的方法制备的片状三氧化二铁的扫描电镜照片，其中图3b的放大倍数大于图3a。如图所示，该方法形成的片状三氧化二铁，形状为六边形，边长约为5μm，厚度约为500nm~1000 nm。
在形成片状三氧化二铁之后，进一步执行以下的步骤S05，以形成片状铁粉。
在步骤S05中，将所述第一粉末进行氢热还原反应，以获得片状铁粉。例如，将液相法合成得到的片状三氧化二铁粉放入管式炉中，在氢气气氛下以350℃~900℃的温度加热0.5~10 h，然后，取出反应物。该反应物即片状铁粉。
图4为根据本发明实施例的方法制备的片状铁粉的XRD图谱。在步骤S05之后，反应产物为Fe。
图5为根据本发明实施例的方法制备的片状铁粉的扫描电镜照片。氢热还原得到的片状铁粉基本保持了片状三氧化二铁的形状和尺寸，片状铁粉的形状为六边形，边长约为5μm。通过原子力显微镜测试可知，片状铁粉的厚度约为500nm~1000 nm。
优选地，在步骤S06中，进行弱酸腐蚀，以减小片状铁粉的尺寸。例如，通过将片状铁粉放入到具有一定浓度的氢氟酸、草酸等弱酸溶液中，可以改变片状铁粉的尺寸。增加弱酸溶液的浓度或增加弱酸刻蚀的时间，都可以使得片状铁粉的尺寸越来越小。通过控制弱酸溶液的浓度或弱酸刻蚀的时间，片状铁粉的边长可以在500nm~5μm之间进行调节，而其厚度可以在50nm~1000 nm之间进行调节。
图6为根据本发明实施例的方法制备的片状铁粉的频率反射损耗关系曲线。采用上述的片状铁粉制备吸波涂层，然后测量不同频率下的反射损耗。该吸波涂层的吸收峰位置对应于有效吸收带，受到涂层厚度和片状铁粉的尺寸的影响。
当片状铁粉的边长为5μm时，其吸波涂层的厚度为1.1mm时，反射损耗可达-15dB, 其有效吸收带位于（＜-10 dB）位于12~17 GHz。当吸波涂料的厚度增加时，吸波峰的位置向低频方向移动。当吸波涂料的厚度在0.9~3 mm之间时，小于-10 dB的反射损耗可在3.6~18 GHz的范围内观测到。
通过改变片状铁粉的尺寸可以调节吸收峰的位置。当片状铁粉的边长减小时，相同铁粉质量分数下的吸波涂层的吸收峰的位置向高频方向移动。上述结果说明，基于上述方法制备的片状铁粉的吸波涂料具有优异的吸波性能，表明上述方法制备的片状铁粉是优良的波的吸收剂。
根据本发明的另一方面，提供一种吸波涂料。吸波涂料至少包括成膜物质和吸收剂，此外还可以包括添加剂和溶剂，其中，成膜物质例如是树脂，吸收剂例如为片状铁粉。例如，所述的成膜物质为：环氧树脂，聚氨酯，氯磺化聚乙烯等。吸收剂例如为铁氧体、金属粉、多晶/非晶纤维等。该吸波涂料利用片状吸波材料作为吸收剂，由于片状吸波材料的二维结构的形状各向异性，可以突破Snoek极限从而在GHz频段内具有较高的磁导率，因此而获得优异的电磁波吸收性能。
应当说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
最后应说明的是：显然，上述实施例仅仅是为清楚地说明本发明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明的保护范围之中。

Claims (15)

  1. 一种吸波材料的制备方法，其特征在于，所述方法包括：
    形成包括反应原料的混合溶液；
    将所述混合溶液进行液相合成反应；
    将反应后的反应产物进行酸洗除杂；
    在酸洗除杂之后进行清洗干燥，以获得第一粉末；以及
    将所述第一粉末进行氢热还原反应，以获得第二粉末，
    其中，所述第一粉末和所述第二粉末的颗粒均为片状，所述第二粉末为所述吸波材料。
  2. 根据权利要求1所述的方法，其特征在于，所述第一粉末为三氧化二铁粉末，所述反应原料包括Fe(NO 3) 3•9H 2O、Ba(NO 3) 2、NaOH。
  3. 根据权利要求2所述的方法，其特征在于，Fe(NO 3) 3•9H 2O、Ba(NO 3) 2、NaOH的质量配比为：1~10∶0.05~0.5∶0.5~5。
  4. 根据权利要求2所述的方法，其特征在于，所述混合溶液的溶剂包括体积比为5∶1~1∶1的水和聚乙二醇，其中，聚乙二醇的分子量为400~1000。
  5. 根据权利要求2所述的方法，其特征在于，所述反应产物包括三氧化二铁和BaCO 3的混合物，在所述将反应后的反应产物进行酸洗除杂的步骤中，通过酸洗除去BaCO 3且保留三氧化二铁。
  6. 根据权利要求5所述的方法，其特征在于，所述酸洗采用浓度为0.5~5 mol/L的盐酸，浸入时长为10~30h。
  7. 根据权利要求1所述的方法，其特征在于，所述第二粉末为铁粉。
  8. 根据权利要求1所述的方法，其特征在于，所述将所述混合溶液进行液相合成反应的步骤包括：
    将所述混合溶液搅拌20分钟至1小时后放入水热反应釜中；
    将所述水热反应釜在160℃~220℃温度下加热10~50h后，降至室温并取出所述反应产物。
  9. 根据权利要求1所述的方法，其特征在于，所述将所述第一粉末进行氢热还原反应的步骤包括：
    将所述第一粉末放入管式炉中，并在氢气中以350℃~900℃的温度加热0.5h~10h。
  10. 根据权利要求1所述的方法，其特征在于，在将所述第一粉末进行氢热还原反应之后，所述方法还包括：
    进行弱酸腐蚀，以减小所述第二粉末的尺寸。
  11. 根据权利要求10所述的方法，其特征在于，所述弱酸包括选自氢氟酸和草酸中的至少一种。
  12. 根据权利要求10所述的方法，其特征在于，所述弱酸腐蚀使得所述第二粉末的颗粒片的厚度和边长中的至少一个减小。
  13. 一种吸波涂料，其特征在于，所述吸波涂料包括：
    成膜物质；以及
    吸收剂；
    其中，所述吸收剂为根据权利要求1-12中任一项所述的方法制备的吸波材料。
  14. 根据权利要求13所述的方法，其特征在于，所述成膜物质为树脂。
  15. 根据权利要求13所述的方法，其特征在于，所述吸波材料为片状的铁粉末。
     
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CN113980464B (zh) * 2021-11-23 2024-05-07 深圳市北测检测技术有限公司 一种基于Fe4N制备Fe4N@PANI纳米复合吸波材料的方法
CN114163820A (zh) * 2021-12-17 2022-03-11 成都佳驰电子科技股份有限公司 一种双组分加成型硅胶吸波薄膜及其制备方法
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CN115007854A (zh) * 2022-07-08 2022-09-06 重庆邮电大学 一种二氧化硅薄层包覆FeSiAl合金微粉的电磁吸收剂的制备方法及其产品和应用
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CN116395750A (zh) * 2023-03-27 2023-07-07 桂林电子科技大学 一种SmCaFeO吸波材料及其制备方法
CN116655384A (zh) * 2023-06-07 2023-08-29 徐州工程学院 一种耐高温高熵吸波陶瓷及其制备方法和应用
CN116655384B (zh) * 2023-06-07 2023-12-12 徐州工程学院 一种耐高温高熵吸波陶瓷及其制备方法和应用

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