WO2019127991A1 - Wave-absorbing agent and preparation method therefor - Google Patents

Wave-absorbing agent and preparation method therefor Download PDF

Info

Publication number
WO2019127991A1
WO2019127991A1 PCT/CN2018/083696 CN2018083696W WO2019127991A1 WO 2019127991 A1 WO2019127991 A1 WO 2019127991A1 CN 2018083696 W CN2018083696 W CN 2018083696W WO 2019127991 A1 WO2019127991 A1 WO 2019127991A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron powder
carbonyl iron
parts
butyl titanate
absorbing agent
Prior art date
Application number
PCT/CN2018/083696
Other languages
French (fr)
Chinese (zh)
Inventor
刘若鹏
赵治亚
林白阁
Original Assignee
洛阳尖端技术研究院
洛阳尖端装备技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 洛阳尖端技术研究院, 洛阳尖端装备技术有限公司 filed Critical 洛阳尖端技术研究院
Publication of WO2019127991A1 publication Critical patent/WO2019127991A1/en

Links

Images

Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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
    • 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

Definitions

  • the invention relates to an absorbing material, and more particularly to a Fe/BaTiO 3 core-shell material absorbing agent and a preparation method thereof.
  • Electromagnetic technology has brought great convenience to people, and it has also caused serious electromagnetic radiation pollution. Electromagnetic radiation not only interferes with electronic instruments and equipment, causing it to malfunction, but also affects human health, interferes with normal physiological functions of the human body, and may even cause diseases. Therefore, absorbing materials for electromagnetic pollution have emerged.
  • carbonyl iron powder As a typical magnetic loss absorbing material, carbonyl iron powder has the advantages of thin matching thickness, good absorption effect in intermediate frequency band and excellent thermal stability, but also low frequency (less than or equal to 5 GHz) absorption effect, easy to be oxidized and loss mechanism. A single disadvantage.
  • the present invention has surface-modified carbonyl iron powder by BaTiO 3 and prepared a composite absorbing wave of BaTiO 3 surface-modified carbonyl iron powder by sol-gel method. Agent.
  • the present invention provides a method of preparing a absorbing agent, the method comprising:
  • the pretreated carbonyl iron powder is prepared by the following method:
  • Polyvinylpyrrolidone and carbonyl iron powder were added to the second deionized water, stirred, and separated to obtain a pretreated carbonyl iron powder.
  • the mass ratio of the second deionized water, the polyvinylpyrrolidone and the carbonyl iron powder is from 450 to 550:5 to 15:3 to 8.
  • the mass ratio of the ethanol, the butyl titanate, and the acetic acid is 4 to 6:3 to 5:6 to 8.
  • the mass ratio of the first deionized water to the cerium acetate is from 5 to 9:2 to 3.
  • the mass ratio of the aqueous solution of cerium acetate, the mixed solution of butyl titanate acetate, and the pretreated carbonyl iron powder is from 10 to 15:6 to 10:0.5 to 25.
  • the pH adjustment is adjusted to a pH of 3 to 5, and the acetic acid is added at a temperature of 50 to 70 ° C, and the temperature T is 60 to 80 °C.
  • the stirring speed is 600 to 800 r/min; and the stirring time is 10 to 30 minutes.
  • the calcination temperature is 800 to 900 ° C
  • the calcination time is 1 to 3 h.
  • the present invention also provides a wave absorbing agent prepared according to the above method.
  • the invention forms a composite material by introducing BaTiO 3 into a carbonyl iron powder absorbing agent by surface modification, wherein the surface modification method can effectively improve the physical and chemical properties of the surface of the material, improve the surface activity and stability, and impart new electromagnetic to the particles.
  • the characteristics, thus significantly improving the low-frequency absorbing properties of the absorbing agent, and making the prepared absorbing agent have better absorbing properties in the range of 2 to 5 GHz.
  • Figure 1 is a flow chart for preparing a Fe/BaTiO 3 core-shell material absorbing agent.
  • BaTiO 3 is a perovskite type ferroelectric with high dielectric constant and excellent piezoelectricity. Under the action of electromagnetic field, it mainly depends on the orientation polarization of the electric dipole and the electromagnetic wave of the interface polarization loss. It is good. Dielectric loss type absorbing material.
  • the invention synthesizes BaTiO 3 by the sol-gel method and coats it onto the surface of the carbonyl iron powder, thereby effectively improving the electromagnetic characteristics and the absorbing properties of the composite absorbing agent.
  • the invention provides a method for preparing a Fe/BaTiO 3 core-shell material absorbing agent, the method comprising the following steps:
  • a container such as a beaker
  • 450-550 parts of deionized water, 5-15 parts of polyvinylpyrrolidone and 3-8 parts of carbonyl iron powder are sequentially added, and the mixture is electrically stirred at 600-800 r/min for 7-9 hours, 300 ⁇ 600 W of power magnetic separation to obtain pretreated carbonyl iron powder;
  • the pretreated carbonyl iron powder can be easily Adsorbing the sol; then stirring at a speed of 600-800 r/min for 10-30 min, centrifuging at 800-1000 r/min, washing the carbonyl iron powder adsorbing the sol with ethanol, and placing the carbonyl iron powder adsorbing the sol on the surface at 50 ⁇ 90°C drying oven for 2 ⁇ 5h, finally placed in a vacuum tube furnace and calcined at 800 ⁇ 900°C for 1-3h. After cooling, Fe/BaTiO 3 core shell material absorbing agent is obtained.
  • the carbonyl iron powder is effectively compounded with BaTiO 3 by calcining at a temperature of 800 to 900 ° C for 1 to 3 hours.
  • the Fe/BaTiO 3 core-shell absorbing material can be efficiently prepared by adding pretreated carbonyl iron powder to the sol system.
  • carbonyl iron powder has the advantages of thin matching thickness, good absorption effect in the intermediate frequency band and excellent thermal stability.
  • BaTiO 3 is a perovskite type ferroelectric with high dielectric constant and excellent piezoelectricity. Under the action of electromagnetic field, it mainly depends on the orientation polarization of the electric dipole and the electromagnetic wave of the interface polarization loss. It is good.
  • the dielectric loss type absorbing material therefore, the present invention can obtain a material having good low frequency absorbing properties by adjusting the ratio of the two components.
  • the Fe/BaTiO 3 core-shell material after the composite dielectric loss material BaTiO 3 can enhance the dielectric loss of the carbonyl iron powder, so that the imaginary part of the dielectric constant of the carbonyl iron powder is significantly increased.
  • the magnetic permeability of the composite Fe/BaTiO 3 core-shell material decreases to lower the magnetic loss, thus improving the impedance matching performance of the composite.
  • the electromagnetic wave can enter the inside of the material more effectively without being reflected, thereby improving the absorbing properties of the material, when the ratio of BaTiO 3 or carbonyl iron powder Too high or too low will affect the impedance matching of the prepared composite material, which in turn affects the absorbing properties of the material.
  • the influence of the stirring speed and time of the carbonyl iron powder added into the sol on the electromagnetic properties of the core-shell material powder can obtain a material with excellent electromagnetic properties by adjusting the mixing time of the two components at a certain stirring rate.
  • the sufficient stirring time can form a large number of interaction interfaces between the flaky carbonyl iron powder and BaTiO 3 , enhance the interfacial polarization of different dielectric particles, and promote the different degrees of improvement of the real and imaginary parts of the dielectric constant. Therefore, different mixing times can make the coating amount of the core-shell structure different.
  • the stirring time is at 600-800 r/min. Should be controlled at 10 to 30 minutes.
  • butyl titanate acetate 4 parts was added to 5 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 60 ° C, and then 7 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetate;
  • butyl titanate acetic acid 4 parts was added to 5 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 55 ° C, and then 6 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetic acid;
  • cerium acetate Adding 3 parts of cerium acetate to 5 to 9 parts of deionized water, heating to 70 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
  • Example Peak frequency Maximum reflection loss ⁇ -10dB bandwidth 1 4GHz -14.68dB 2.75GHz 2 3.5GHz -13.26dB 2.31GHz 3 3.1GHz -12.68dB 1.92GHz 4 3.7GHz -13.65dB 2.02GHz 5 3.2GHz -14.21dB 1.96GHz 6 3.6GHz -12.95dB 2.26GHz
  • the Fe/BaTiO 3 core-shell material absorbing agent prepared by the method of the invention effectively increases the absorbing property of the carbonyl iron powder, so that the maximum reflection loss at low frequency (less than or equal to 5 GHz) is as low as - 14.68dB, because BaTiO 3 is a perovskite type ferroelectric with high dielectric constant and excellent piezoelectricity.
  • the lossy electromagnetic wave is a good dielectric loss type absorbing material.
  • the sol-gel method combines the magnetic loss type material carbonyl iron powder with the dielectric loss material BaTiO 3 to effectively improve the impedance matching performance of the material and improve the low frequency band. Absorbing performance.
  • BaTiO 3 is a dielectric material, which can significantly increase the dielectric constant of the composite when combined with carbonyl iron powder.
  • the absorbing agent prepared by the invention can be applied to the technical fields of mobile phone, electronic equipment, high-frequency equipment, microwave active device, clutter suppression and anti-electromagnetic interference of radar and microwave communication systems; Stealth, ship stealth, flight missile stealth, and tank stealth.

Abstract

Provided are a method for preparing a wave-absorbing agent and a wave-absorbing agent obtained thereby. The method comprises: adding butyl titanate to ethanol, followed by addition of acetic acid so as to obtain a mixed liquid of butyl titanate and acetic acid; adding barium acetate to first deionized water, heating same to a temperature T so as to obtain a barium acetate aqueous solution; and adding the barium acetate aqueous solution to the mixed liquid of butyl titanate and acetic acid to form a sol, the pH value of which is adjusted, and adding a pretreated carbonyl iron powder, stirring, centrifuging, drying and calcining same so as to obtain the wave-absorbing agent. The wave-absorbing agent prepared by the method significantly enhances the low frequency absorbing performance, with the wave-absorbing performance in the range 2-5 GHz being better.

Description

一种吸波剂及其制备方法Absorbing agent and preparation method thereof 技术领域Technical field
本发明涉及吸波材料，更具体地，涉及一种Fe/BaTiO 3核壳材料吸波剂及其制备方法。 The invention relates to an absorbing material, and more particularly to a Fe/BaTiO 3 core-shell material absorbing agent and a preparation method thereof.
背景技术Background technique
随着电子科学技术的发展，电子信息设备在各行各业都得到了广泛的应用。电磁波对人类的影响也已渗透到各个角落。其在机械、电子、生物领域都是不可替代的。电磁技术给人们带来了极大的便利的同时，也严重引来了的严重的电磁福射污染。电磁福射不仅会干扰电子仪器和设备，导致其不能正常运转，还会影响人类的身体健康，干扰人体正常生理机能，甚至可能导致疾病。因此，治理电磁污染的吸波材料应运而生。With the development of electronic science and technology, electronic information equipment has been widely used in various industries. The effects of electromagnetic waves on humans have also penetrated into every corner. It is irreplaceable in the fields of machinery, electronics and biology. Electromagnetic technology has brought great convenience to people, and it has also caused serious electromagnetic radiation pollution. Electromagnetic radiation not only interferes with electronic instruments and equipment, causing it to malfunction, but also affects human health, interferes with normal physiological functions of the human body, and may even cause diseases. Therefore, absorbing materials for electromagnetic pollution have emerged.
羰基铁粉作为典型磁损耗型吸波材料，具有匹配厚度薄、中频波段吸收效果好和优异的热稳定性等优点，但也存在低频(小于等于5GHz)吸收效果差、易被氧化及损耗机制单一的缺点。As a typical magnetic loss absorbing material, carbonyl iron powder has the advantages of thin matching thickness, good absorption effect in intermediate frequency band and excellent thermal stability, but also low frequency (less than or equal to 5 GHz) absorption effect, easy to be oxidized and loss mechanism. A single disadvantage.
发明内容Summary of the invention
针对以上问题，为了进一步改善羰基铁粉的低频吸波性能，本发明通过BaTiO 3对羰基铁粉表面改性，并且采用溶胶-凝胶法制备了BaTiO 3表面改性羰基铁粉的复合吸波剂。 In order to further improve the low-frequency absorbing properties of carbonyl iron powder, the present invention has surface-modified carbonyl iron powder by BaTiO 3 and prepared a composite absorbing wave of BaTiO 3 surface-modified carbonyl iron powder by sol-gel method. Agent.
本发明提供了一种制备吸波剂的方法，所述方法包括：The present invention provides a method of preparing a absorbing agent, the method comprising:
在乙醇中加入钛酸丁酯，得到钛酸丁酯乙醇溶液，再加入乙酸，得到钛酸丁酯乙酸混合液；在第一去离子水中加入乙酸钡，加热至温度T，得到乙酸钡水溶液；以及将所述乙酸钡水溶液加入至所述钛酸丁酯乙酸混合液中，形成溶胶，再调节pH，加入预处理的羰基铁粉，搅拌，离心、干燥、煅烧，得到所述吸波剂。Adding butyl titanate to ethanol to obtain a solution of butyl titanate in ethanol, and then adding acetic acid to obtain a mixture of butyl titanate acetate; adding cerium acetate in the first deionized water and heating to temperature T to obtain an aqueous solution of cerium acetate; And adding the cerium acetate aqueous solution to the butyl titanate acetic acid mixture to form a sol, adjusting the pH, adding the pretreated carbonyl iron powder, stirring, centrifuging, drying, and calcining to obtain the absorbing agent.
在上述方法中，所述预处理的羰基铁粉通过以下方法制备：In the above method, the pretreated carbonyl iron powder is prepared by the following method:
在第二去离子水中加入聚乙烯吡咯烷酮和羰基铁粉，搅拌，分离，得到预处理的羰基铁粉。Polyvinylpyrrolidone and carbonyl iron powder were added to the second deionized water, stirred, and separated to obtain a pretreated carbonyl iron powder.
在上述方法中，所述第二去离子水、所述聚乙烯吡咯烷酮和所述羰基铁粉的质量比为450～550:5～15:3～8。In the above method, the mass ratio of the second deionized water, the polyvinylpyrrolidone and the carbonyl iron powder is from 450 to 550:5 to 15:3 to 8.
在上述方法中，所述乙醇、所述钛酸丁酯和所述乙酸的质量比为4～6:3～5:6～8。In the above method, the mass ratio of the ethanol, the butyl titanate, and the acetic acid is 4 to 6:3 to 5:6 to 8.
在上述方法中，所述第一去离子水和所述乙酸钡的质量比为5～9:2～3。In the above method, the mass ratio of the first deionized water to the cerium acetate is from 5 to 9:2 to 3.
在上述方法中，所述乙酸钡水溶液、所述钛酸丁酯乙酸混合液和所述预处理的羰基铁粉的质量比为10～15:6～10:0.5～25。In the above method, the mass ratio of the aqueous solution of cerium acetate, the mixed solution of butyl titanate acetate, and the pretreated carbonyl iron powder is from 10 to 15:6 to 10:0.5 to 25.
在上述方法中，所述调节pH将pH值调节为3～5，在50～70℃的温度下加入所述乙酸，所述温度T为60～80℃。In the above method, the pH adjustment is adjusted to a pH of 3 to 5, and the acetic acid is added at a temperature of 50 to 70 ° C, and the temperature T is 60 to 80 °C.
在上述方法中，所述搅拌的转速为600～800r/min；所述搅拌的时间为10～30min。In the above method, the stirring speed is 600 to 800 r/min; and the stirring time is 10 to 30 minutes.
在上述方法中，所述煅烧的温度为800～900℃，所述煅烧的时间为1～3h。In the above method, the calcination temperature is 800 to 900 ° C, and the calcination time is 1 to 3 h.
本发明还提供了一种根据以上方法制备的吸波剂。The present invention also provides a wave absorbing agent prepared according to the above method.
本发明通过将BaTiO 3以表面改性方式引入羰基铁粉吸波剂，形成复合材料，其中，表面改性方法能够有效改善材料表面物理化学性质，提高表面活性及稳定性，赋予粒子新的电磁特性，因而显著提升了吸波剂的低频吸波性能，而且使得制备的吸波剂在2～5GHz范围内吸波性能较好。 The invention forms a composite material by introducing BaTiO 3 into a carbonyl iron powder absorbing agent by surface modification, wherein the surface modification method can effectively improve the physical and chemical properties of the surface of the material, improve the surface activity and stability, and impart new electromagnetic to the particles. The characteristics, thus significantly improving the low-frequency absorbing properties of the absorbing agent, and making the prepared absorbing agent have better absorbing properties in the range of 2 to 5 GHz.
附图说明DRAWINGS
图1是Fe/BaTiO 3核壳材料吸波剂的制备流程图。 Figure 1 is a flow chart for preparing a Fe/BaTiO 3 core-shell material absorbing agent.
具体实施方式Detailed ways
下面的实施例可以使本领域技术人员更全面地理解本发明，但不以任何方式限制本发明。The following examples are intended to provide a more complete understanding of the invention, and are not intended to limit the invention in any way.
近年来，在吸波材料领域，对低频(小于等于5GHz)的有效吸收一直 是研究的重点和难点。BaTiO 3是一种具有高介电常数和优良压电性的钙钛矿型铁电体，在电磁场作用下，其主要依靠电偶极子的取向极化和界面极化损耗电磁波，是良好的介电损耗型吸波材料。本发明通过溶胶-凝胶方法合成BaTiO 3并将其包覆至羰基铁粉表面，有效改善了复合吸波剂的电磁特性及吸波性能。 In recent years, in the field of absorbing materials, the effective absorption of low frequencies (less than or equal to 5 GHz) has been the focus and difficulty of research. BaTiO 3 is a perovskite type ferroelectric with high dielectric constant and excellent piezoelectricity. Under the action of electromagnetic field, it mainly depends on the orientation polarization of the electric dipole and the electromagnetic wave of the interface polarization loss. It is good. Dielectric loss type absorbing material. The invention synthesizes BaTiO 3 by the sol-gel method and coats it onto the surface of the carbonyl iron powder, thereby effectively improving the electromagnetic characteristics and the absorbing properties of the composite absorbing agent.
本发明提供了一种制备Fe/BaTiO 3核壳材料吸波剂的方法，该方法包括以下步骤： The invention provides a method for preparing a Fe/BaTiO 3 core-shell material absorbing agent, the method comprising the following steps:
在容器(如烧杯)中依次加入450～550份去离子水、5～15份聚乙烯吡咯烷酮和3～8份羰基铁粉，以600～800r/min的转速电动搅拌7～9h，以300～600W的功率磁选分离得到预处理的羰基铁粉；In a container (such as a beaker), 450-550 parts of deionized water, 5-15 parts of polyvinylpyrrolidone and 3-8 parts of carbonyl iron powder are sequentially added, and the mixture is electrically stirred at 600-800 r/min for 7-9 hours, 300~ 600 W of power magnetic separation to obtain pretreated carbonyl iron powder;
在4～6份乙醇中加入3～5份钛酸丁酯，以600～800r/min的转速磁力搅拌至液体混合均匀，加热至50～70℃，达到最佳水解温度，然后向溶液中滴加6～8份冰乙酸，以600～800r/min的转速搅拌30～60min，得到钛酸丁酯乙酸混合液；Add 3 to 5 parts of butyl titanate to 4-6 parts of ethanol, magnetically stir at 600-800r/min until the liquid is evenly mixed, heat to 50-70 ° C, reach the optimal hydrolysis temperature, and then drop into the solution. Add 6-8 parts of glacial acetic acid, stir at 600-800r/min for 30-60min to obtain a mixture of butyl titanate acetate;
在5～9份去离子水中加入2～3份乙酸钡，加热至60～80℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Adding 2 to 3 parts of cerium acetate in 5 to 9 parts of deionized water, heating to 60 to 80 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在30～50℃的恒温条件下将10～15份乙酸钡水溶液滴加到6～10份钛酸丁酯乙酸混合液中，直至滴加完全，以600～800r/min的转速磁力搅拌1～2h后形成溶胶，滴加氨水调节pH为3～5，加入0.5～25份预处理的羰基铁粉，在pH为3～5的酸性环境下，可以使预处理羰基铁粉较易地吸附溶胶；然后以600～800r/min的转速搅拌10～30min，以800～1000r/min的转速离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于50～90℃干燥箱中2～5h，最后放入真空管式炉中在800～900℃的温度下煅烧1～3h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 10 to 15 parts of an aqueous solution of cerium acetate is added dropwise to a mixture of 6 to 10 parts of butyl titanate acetic acid at a constant temperature of 30 to 50 ° C until the addition is complete, and magnetic stirring is performed at a rotational speed of 600 to 800 r/min. After 1~2h, the sol is formed, the ammonia is added dropwise to adjust the pH to 3~5, and 0.5~25 parts of the pretreated carbonyl iron powder is added. In the acidic environment with pH of 3-5, the pretreated carbonyl iron powder can be easily Adsorbing the sol; then stirring at a speed of 600-800 r/min for 10-30 min, centrifuging at 800-1000 r/min, washing the carbonyl iron powder adsorbing the sol with ethanol, and placing the carbonyl iron powder adsorbing the sol on the surface at 50 ～90°C drying oven for 2～5h, finally placed in a vacuum tube furnace and calcined at 800～900°C for 1-3h. After cooling, Fe/BaTiO 3 core shell material absorbing agent is obtained.
在以上方法中，通过800～900℃的温度下煅烧1～3h，使得羰基铁粉与BaTiO 3有效地复合。 In the above method, the carbonyl iron powder is effectively compounded with BaTiO 3 by calcining at a temperature of 800 to 900 ° C for 1 to 3 hours.
在以上方法中，BaTiO 3和羰基铁粉的比例对核壳材料吸波性能的影响： In the above method, the effect of the ratio of BaTiO 3 and carbonyl iron powder on the absorbing properties of the core-shell material:
通过向溶胶体系中加入预处理羰基铁粉能够有效制备Fe/BaTiO 3核壳吸波材料。羰基铁粉作为典型磁损耗型吸波材料，具有匹配厚度薄、中频 波段吸收效果好和优异的热稳定性等优点。BaTiO 3是一种具有高介电常数和优良压电性的钙钛矿型铁电体，在电磁场作用下，其主要依靠电偶极子的取向极化和界面极化损耗电磁波，是良好的介电损耗型吸波材料，因此，本发明通过调控两组分的比例可以获得低频吸波性能良好的材料。一方面，复合介电损耗材料BaTiO 3后的Fe/BaTiO 3核壳材料可以提升羰基铁粉的介电损耗能力，使得羰基铁粉的介电常数的虚部得到了显著升高。另一方面，复合后的Fe/BaTiO 3核壳材料的磁导率发生下降使得磁损耗下降，因此改善了复合材料的阻抗匹配性能。材料的阻抗匹配越好，即越接近于自由空间的阻抗值，则电磁波能更有效地进入材料内部而不被反射出去，从而能提高材料的吸波性能，当BaTiO 3或羰基铁粉的比例太高或太低时，都会影响制备的复合材料的阻抗匹配，进而影响材料的吸波性能。 The Fe/BaTiO 3 core-shell absorbing material can be efficiently prepared by adding pretreated carbonyl iron powder to the sol system. As a typical magnetic loss absorbing material, carbonyl iron powder has the advantages of thin matching thickness, good absorption effect in the intermediate frequency band and excellent thermal stability. BaTiO 3 is a perovskite type ferroelectric with high dielectric constant and excellent piezoelectricity. Under the action of electromagnetic field, it mainly depends on the orientation polarization of the electric dipole and the electromagnetic wave of the interface polarization loss. It is good. The dielectric loss type absorbing material, therefore, the present invention can obtain a material having good low frequency absorbing properties by adjusting the ratio of the two components. On the one hand, the Fe/BaTiO 3 core-shell material after the composite dielectric loss material BaTiO 3 can enhance the dielectric loss of the carbonyl iron powder, so that the imaginary part of the dielectric constant of the carbonyl iron powder is significantly increased. On the other hand, the magnetic permeability of the composite Fe/BaTiO 3 core-shell material decreases to lower the magnetic loss, thus improving the impedance matching performance of the composite. The better the impedance matching of the material, that is, the closer to the impedance value of the free space, the electromagnetic wave can enter the inside of the material more effectively without being reflected, thereby improving the absorbing properties of the material, when the ratio of BaTiO 3 or carbonyl iron powder Too high or too low will affect the impedance matching of the prepared composite material, which in turn affects the absorbing properties of the material.
在以上方法中，羰基铁粉加入溶胶中的搅拌转速和时间对核壳材料粉体电磁性能的影响，通过调控两组份的在一定搅拌速率下的混合搅拌时间可以获得电磁性能优异良好的材料。充分的搅拌时间能够使片状羰基铁粉与BaTiO 3形成大量交互界面，增强了不同介质粒子的界面极化，进而促进介电常数实部和虚部不同程度的提升。因此，搅拌时间不同，可以使得核壳结构的包覆量存在差异，当搅拌时间太短时，包覆量较小，使得BaTiO 3颗粒较小，表面容易吸附大量石蜡，从而导致铁粉之间产生渗漏电现象，出现介电常数显著增大的现象；当搅拌时间增加时，包覆量增加，BaTiO 3颗粒相互团聚降低了与石蜡的吸附，从而介电常数较低；当搅拌时间过长时，会影响BaTiO 3颗粒的相互团聚，从而使得BaTiO 3颗粒的表面容易吸附大量石蜡，从而导致铁粉之间产生渗漏电现象，因此，在600～800r/min的转速下，搅拌时间应控制在10～30min。 In the above method, the influence of the stirring speed and time of the carbonyl iron powder added into the sol on the electromagnetic properties of the core-shell material powder can obtain a material with excellent electromagnetic properties by adjusting the mixing time of the two components at a certain stirring rate. . The sufficient stirring time can form a large number of interaction interfaces between the flaky carbonyl iron powder and BaTiO 3 , enhance the interfacial polarization of different dielectric particles, and promote the different degrees of improvement of the real and imaginary parts of the dielectric constant. Therefore, different mixing times can make the coating amount of the core-shell structure different. When the stirring time is too short, the coating amount is small, so that the BaTiO 3 particles are small, and the surface is easy to adsorb a large amount of paraffin, thereby causing iron powder between Leakage phenomenon occurs, and the dielectric constant increases remarkably; when the stirring time increases, the coating amount increases, and the agglomeration of BaTiO 3 particles reduces the adsorption with paraffin, and the dielectric constant is low; When it is long, it will affect the mutual agglomeration of BaTiO 3 particles, so that the surface of BaTiO 3 particles can easily adsorb a large amount of paraffin, which causes leakage between the iron powders. Therefore, the stirring time is at 600-800 r/min. Should be controlled at 10 to 30 minutes.
实施例1Example 1
在烧杯中依次加入500份去离子水、10份聚乙烯吡咯烷酮和5份羰基铁粉，电动搅拌、磁选分离得到预处理的羰基铁粉；500 parts of deionized water, 10 parts of polyvinylpyrrolidone and 5 parts of carbonyl iron powder were sequentially added to the beaker, and the pretreated carbonyl iron powder was obtained by electric stirring and magnetic separation;
在5份乙醇中加入4份钛酸丁酯，磁力搅拌至液体混合均匀，加热至60℃，然后向溶液中滴加7份冰乙酸，搅拌，得到钛酸丁酯乙酸混合液；4 parts of butyl titanate was added to 5 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 60 ° C, and then 7 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetate;
在7份去离子水中加入2份乙酸钡，加热至70℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Adding 2 parts of cerium acetate to 7 parts of deionized water, heating to 70 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在40℃的恒温条件下将12份乙酸钡水溶液滴加到8份钛酸丁酯乙酸混合液中，直至滴加完全，磁力搅拌1h后形成溶胶，滴加氨水调节pH为4，加入25份预处理的羰基铁粉，搅拌10min，离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于70℃干燥箱中4h，最后放入真空管式炉中在850℃的温度下煅烧2h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 12 parts of an aqueous solution of cerium acetate was added dropwise to a mixture of 8 parts of butyl titanate acetic acid under a constant temperature of 40 ° C until the addition was complete, magnetic stirring was performed for 1 hour to form a sol, and ammonia was added dropwise to adjust the pH to 4, and then added. 25 pretreated carbonyl iron powder, stirred for 10 min, centrifuged and washed with ethanol to wash the carbonyl iron powder on the surface of the sol, and then the carbonyl iron powder adsorbing the sol on the surface was placed in a drying oven at 70 ° C for 4 h, and finally placed in a vacuum tube furnace. It was calcined at a temperature of 850 ° C for 2 h, and after cooling, a Fe/BaTiO 3 core-shell material absorbing agent was obtained.
实施例2Example 2
在烧杯中依次加入520份去离子水、12份聚乙烯吡咯烷酮和4份羰基铁粉，电动搅拌、磁选分离得到预处理的羰基铁粉；520 parts of deionized water, 12 parts of polyvinylpyrrolidone and 4 parts of carbonyl iron powder were sequentially added to the beaker, and the pretreated carbonyl iron powder was obtained by electric stirring and magnetic separation;
在5份乙醇中加入4份钛酸丁酯，磁力搅拌至液体混合均匀，加热至55℃，然后向溶液中滴加6份冰乙酸，搅拌，得到钛酸丁酯乙酸混合液；4 parts of butyl titanate was added to 5 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 55 ° C, and then 6 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetic acid;
在5～9份去离子水中加入3份乙酸钡，加热至70℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Adding 3 parts of cerium acetate to 5 to 9 parts of deionized water, heating to 70 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在45℃的恒温条件下将12份乙酸钡水溶液滴加到8份钛酸丁酯乙酸混合液中，直至滴加完全，磁力搅拌1.5h后形成溶胶，滴加氨水调节pH为3，加入15份预处理的羰基铁粉，搅拌20min，离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于70℃干燥箱中2～5h，最后放入真空管式炉中在820℃的温度下煅烧2h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 12 parts of an aqueous solution of cerium acetate was added dropwise to 8 parts of a mixture of butyl titanate acetate at a constant temperature of 45 ° C until the addition was complete, magnetic stirring was carried out for 1.5 hours to form a sol, and aqueous ammonia was added dropwise to adjust the pH to 3. Add 15 parts of pretreated carbonyl iron powder, stir for 20min, centrifuge and wash the carbonyl iron powder adsorbing sol on the surface with ethanol, then place the carbonyl iron powder adsorbing the sol on the surface in a drying oven at 70 °C for 2 to 5 hours, and finally put it into the vacuum tube. The furnace was calcined at a temperature of 820 ° C for 2 h, and cooled to obtain a Fe/BaTiO 3 core-shell material absorbing agent.
实施例3Example 3
在烧杯中依次加入520份去离子水、8份聚乙烯吡咯烷酮和4份羰基铁粉，电动搅拌、磁选分离得到预处理的羰基铁粉；520 parts of deionized water, 8 parts of polyvinylpyrrolidone and 4 parts of carbonyl iron powder were sequentially added to the beaker, and the pretreated carbonyl iron powder was obtained by electric stirring and magnetic separation;
在5份乙醇中加入5份钛酸丁酯，磁力搅拌至液体混合均匀，加热至60℃，然后向溶液中滴加7份冰乙酸，搅拌，得到钛酸丁酯乙酸混合液；5 parts of butyl titanate was added to 5 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 60 ° C, and then 7 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetate;
在8份去离子水中加入3份乙酸钡，加热至75℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Add 3 parts of cerium acetate to 8 parts of deionized water, heat to 75 ° C, and fully dissolve the cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在45℃的恒温条件下将11份乙酸钡水溶液滴加到8份钛酸丁 酯乙酸混合液中，直至滴加完全，磁力搅拌2h后形成溶胶，滴加氨水调节pH为5，加入10份预处理的羰基铁粉，搅拌30min，离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于70℃干燥箱中4h，最后放入真空管式炉中在810℃的温度下煅烧2h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 11 parts of an aqueous solution of cerium acetate was added dropwise to 8 parts of a mixture of butyl titanate acetate at a constant temperature of 45 ° C until the addition was complete, magnetic stirring for 2 hours to form a sol, and ammonia was added dropwise to adjust the pH to 5, and added. 10 pretreated carbonyl iron powder, stirred for 30min, centrifuged and washed with ethanol to wash the carbonyl iron powder on the surface, then the carbonyl iron powder adsorbing the sol on the surface was placed in a drying oven at 70 ° C for 4 h, and finally placed in a vacuum tube furnace. It was calcined at a temperature of 810 ° C for 2 h, and after cooling, a Fe/BaTiO 3 core-shell material absorbing agent was obtained.
实施例4Example 4
在烧杯中依次加入450份去离子水、5份聚乙烯吡咯烷酮和3份羰基铁粉，电动搅拌、磁选分离得到预处理的羰基铁粉；450 parts of deionized water, 5 parts of polyvinylpyrrolidone and 3 parts of carbonyl iron powder were sequentially added to the beaker, and the pretreated carbonyl iron powder was obtained by electric stirring and magnetic separation;
在4份乙醇中加入3份钛酸丁酯，磁力搅拌至液体混合均匀，加热至50℃，然后向溶液中滴加6份冰乙酸，搅拌，得到钛酸丁酯乙酸混合液；3 parts of butyl titanate was added to 4 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 50 ° C, and then 6 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetic acid;
在5份去离子水中加入2份乙酸钡，加热至60℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Adding 2 parts of cerium acetate to 5 parts of deionized water, heating to 60 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在30℃的恒温条件下将10份乙酸钡水溶液滴加到6份钛酸丁酯乙酸混合液中，直至滴加完全，磁力搅拌1h后形成溶胶，滴加氨水调节pH为4，加入0.5份预处理的羰基铁粉，搅拌10min，离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于50℃干燥箱中2h，最后放入真空管式炉中在800℃的温度下煅烧1h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 10 parts of an aqueous solution of cerium acetate was added dropwise to 6 parts of a mixture of butyl titanate acetate at a constant temperature of 30 ° C until the addition was complete, magnetic stirring for 1 h, a sol was formed, and ammonia was added dropwise to adjust the pH to 4, and added. 0.5 parts of pretreated carbonyl iron powder, stirred for 10 min, centrifuged and washed with carbonyl iron powder on the surface adsorption sol, and then placed the carbonyl iron powder adsorbed on the surface in a drying oven at 50 ° C for 2 h, and finally placed in a vacuum tube furnace. After calcination at 800 ° C for 1 h, the Fe/BaTiO 3 core-shell material absorbing agent was obtained after cooling.
实施例5Example 5
在烧杯中依次加入550份去离子水、15份聚乙烯吡咯烷酮和8份羰基铁粉，电动搅拌、磁选分离得到预处理的羰基铁粉；550 parts of deionized water, 15 parts of polyvinylpyrrolidone and 8 parts of carbonyl iron powder were sequentially added to the beaker, and the pretreated carbonyl iron powder was obtained by electric stirring and magnetic separation;
在6份乙醇中加入5份钛酸丁酯，磁力搅拌至液体混合均匀，加热至70℃，然后向溶液中滴加8份冰乙酸，搅拌，得到钛酸丁酯乙酸混合液；5 parts of butyl titanate was added to 6 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 70 ° C, and then 8 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetate;
在9份去离子水中加入3份乙酸钡，加热至80℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Adding 3 parts of cerium acetate to 9 parts of deionized water, heating to 80 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在50℃的恒温条件下将15份乙酸钡水溶液滴加到10份钛酸丁酯乙酸混合液中，直至滴加完全，磁力搅拌3h后形成溶胶，滴加氨水调节pH为4，加入5份预处理的羰基铁粉，搅拌30min，离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于90℃干 燥箱中5h，最后放入真空管式炉中在900℃的温度下煅烧3h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 15 parts of an aqueous solution of cerium acetate was added dropwise to 10 parts of a mixture of butyl titanate acetate at a constant temperature of 50 ° C until the addition was complete, magnetic stirring was carried out for 3 hours to form a sol, and ammonia was added dropwise to adjust the pH to 4, and added. 5 pretreated carbonyl iron powder, stirred for 30min, centrifuged and washed with ethanol to wash the carbonyl iron powder on the surface, then the carbonyl iron powder adsorbing the sol on the surface was placed in a 90 ° C drying oven for 5 h, and finally placed in a vacuum tube furnace. After calcination at 900 ° C for 3 h, the Fe/BaTiO 3 core-shell material absorbing agent was prepared after cooling.
实施例6Example 6
在烧杯中依次加入450份去离子水、5份聚乙烯吡咯烷酮和3份羰基铁粉，电动搅拌、磁选分离得到预处理的羰基铁粉；450 parts of deionized water, 5 parts of polyvinylpyrrolidone and 3 parts of carbonyl iron powder were sequentially added to the beaker, and the pretreated carbonyl iron powder was obtained by electric stirring and magnetic separation;
在4份乙醇中加入3份钛酸丁酯，磁力搅拌至液体混合均匀，加热至50℃，然后向溶液中滴加6份冰乙酸，搅拌，得到钛酸丁酯乙酸混合液；3 parts of butyl titanate was added to 4 parts of ethanol, magnetically stirred until the liquid was uniformly mixed, heated to 50 ° C, and then 6 parts of glacial acetic acid was added dropwise to the solution, and stirred to obtain a mixture of butyl titanate acetic acid;
在5份去离子水中加入2份乙酸钡，加热至60℃，使乙酸钡充分溶解，得到乙酸钡水溶液；Adding 2 parts of cerium acetate to 5 parts of deionized water, heating to 60 ° C, and fully dissolving cerium acetate to obtain an aqueous solution of cerium acetate;
之后，在30℃的恒温条件下将10份乙酸钡水溶液滴加到6份钛酸丁酯乙酸混合液中，直至滴加完全，磁力搅拌1h后形成溶胶，滴加氨水调节pH为4，加入1份预处理的羰基铁粉，搅拌10min，离心分离并用乙醇清洗表面吸附溶胶的羰基铁粉，再将表面吸附溶胶的羰基铁粉置于90℃干燥箱中2h，最后放入真空管式炉中在800℃的温度下煅烧3h，冷却后制得Fe/BaTiO 3核壳材料吸波剂。 Thereafter, 10 parts of an aqueous solution of cerium acetate was added dropwise to 6 parts of a mixture of butyl titanate acetate at a constant temperature of 30 ° C until the addition was complete, magnetic stirring for 1 h, a sol was formed, and ammonia was added dropwise to adjust the pH to 4, and added. 1 part of pretreated carbonyl iron powder, stirred for 10min, centrifuged and washed with carbon to wash the surface of the sol-coated carbonyl iron powder, and then the surface of the sol-coated carbonyl iron powder was placed in a 90 ° C drying oven for 2 h, and finally placed in a vacuum tube furnace After calcination at 800 ° C for 3 h, the Fe/BaTiO 3 core-shell material absorbing agent was prepared after cooling.
以上份数均为质量份。The above parts are all parts by mass.
采用本领域中常用的方法测试实施例1至实施例6中制备的Fe/BaTiO 3核壳材料吸波剂在2～6GHz频段内的吸波性能。 The absorbing properties of the Fe/BaTiO 3 core-shell absorbing agent prepared in Examples 1 to 6 in the frequency range of 2 to 6 GHz were tested by methods commonly used in the art.
测试结果如下表1所示：The test results are shown in Table 1 below:
实施例Example 峰值所在频率Peak frequency 最大反射损耗Maximum reflection loss ≤-10dB的频宽≤-10dB bandwidth
11 4GHz4GHz -14.68dB-14.68dB 2.75GHz2.75GHz
22 3.5GHz3.5GHz -13.26dB-13.26dB 2.31GHz2.31GHz
33 3.1GHz3.1GHz -12.68dB-12.68dB 1.92GHz1.92GHz
44 3.7GHz3.7GHz -13.65dB-13.65dB 2.02GHz2.02GHz
55 3.2GHz3.2GHz -14.21dB-14.21dB 1.96GHz1.96GHz
66 3.6GHz3.6GHz -12.95dB-12.95dB 2.26GHz2.26GHz
由上表1可知，根据本发明的方法制备的Fe/BaTiO 3核壳材料吸波剂有效增加了羰基铁粉的吸波性能，使得其在低频(小于等于5GHz)的最大 反射损耗低至-14.68dB，这是由于BaTiO 3是一种具有高介电常数和优良压电性的钙钛矿型铁电体，在电磁场作用下，其主要依靠电偶极子的取向极化和界面极化损耗电磁波，是良好的介电损耗型吸波材料，通过溶胶-凝胶方法将磁损耗型材料羰基铁粉与介电损耗材料BaTiO 3相结合能够有效改善材料的阻抗匹配性能，提高低频段的吸波性能。 It can be seen from the above Table 1 that the Fe/BaTiO 3 core-shell material absorbing agent prepared by the method of the invention effectively increases the absorbing property of the carbonyl iron powder, so that the maximum reflection loss at low frequency (less than or equal to 5 GHz) is as low as - 14.68dB, because BaTiO 3 is a perovskite type ferroelectric with high dielectric constant and excellent piezoelectricity. Under the action of electromagnetic field, it mainly depends on the orientation polarization and interfacial polarization of electric dipole. The lossy electromagnetic wave is a good dielectric loss type absorbing material. The sol-gel method combines the magnetic loss type material carbonyl iron powder with the dielectric loss material BaTiO 3 to effectively improve the impedance matching performance of the material and improve the low frequency band. Absorbing performance.
此外，BaTiO 3属于介电材料，与羰基铁粉复合后能够显著提升复合材料的介电常数。 In addition, BaTiO 3 is a dielectric material, which can significantly increase the dielectric constant of the composite when combined with carbonyl iron powder.
综上，本发明制备的吸波剂可应用于手机、电子仪器设备、高频设备、微波有源器件、雷达及微波通信***的杂波抑制、抗电磁干扰等技术领域；还可以应用于飞机隐身、舰船隐身、飞行导弹隐身以及坦克隐身等领域。In summary, the absorbing agent prepared by the invention can be applied to the technical fields of mobile phone, electronic equipment, high-frequency equipment, microwave active device, clutter suppression and anti-electromagnetic interference of radar and microwave communication systems; Stealth, ship stealth, flight missile stealth, and tank stealth.
本领域技术人员应理解，以上实施例仅是示例性实施例，在不背离本发明的精神和范围的情况下，可以进行多种变化、替换以及改变。Those skilled in the art will appreciate that the above-described embodiments are merely exemplary embodiments, and various changes, substitutions and changes may be made without departing from the spirit and scope of the invention.

Claims (10)

  1. 一种制备吸波剂的方法，其特征在于，所述方法包括：A method of preparing a absorbing agent, the method comprising:
    在乙醇中加入钛酸丁酯，得到钛酸丁酯乙醇溶液，再加入乙酸，得到钛酸丁酯乙酸混合液；Adding butyl titanate to ethanol to obtain a solution of butyl titanate in ethanol, and then adding acetic acid to obtain a mixture of butyl titanate acetate;
    在第一去离子水中加入乙酸钡，加热至温度T，得到乙酸钡水溶液；以及Adding cerium acetate to the first deionized water and heating to a temperature T to obtain an aqueous solution of cerium acetate;
    将所述乙酸钡水溶液加入至所述钛酸丁酯乙酸混合液中，形成溶胶，再调节pH，加入预处理的羰基铁粉，搅拌，离心、干燥、煅烧，得到所述吸波剂。The aqueous solution of cerium acetate is added to the mixed solution of butyl titanate acetic acid to form a sol, and the pH is adjusted, and the pretreated carbonyl iron powder is added, stirred, centrifuged, dried, and calcined to obtain the absorbing agent.
  2. 根据权利要求1所述的方法，其特征在于，所述预处理的羰基铁粉通过以下方法制备：The method of claim 1 wherein said pretreated carbonyl iron powder is prepared by the following method:
    在第二去离子水中加入聚乙烯吡咯烷酮和羰基铁粉，搅拌，分离，得到预处理的羰基铁粉。Polyvinylpyrrolidone and carbonyl iron powder were added to the second deionized water, stirred, and separated to obtain a pretreated carbonyl iron powder.
  3. 根据权利要求2所述的方法，其特征在于，所述第二去离子水、所述聚乙烯吡咯烷酮和所述羰基铁粉的质量比为450～550:5～15:3～8。The method according to claim 2, wherein the mass ratio of the second deionized water, the polyvinylpyrrolidone and the carbonyl iron powder is from 450 to 550:5 to 15:3 to 8.
  4. 根据权利要求1所述的方法，其特征在于，所述乙醇、所述钛酸丁酯和所述乙酸的质量比为4～6:3～5:6～8。The method according to claim 1, wherein the mass ratio of the ethanol, the butyl titanate and the acetic acid is from 4 to 6:3 to 5:6 to 8.
  5. 根据权利要求1所述的方法，其特征在于，所述第一去离子水和所述乙酸钡的质量比为5～9:2～3。The method according to claim 1, wherein the mass ratio of the first deionized water to the cerium acetate is from 5 to 9:2 to 3.
  6. 根据权利要求1所述的方法，其特征在于，所述乙酸钡水溶液、所述钛酸丁酯乙酸混合液和所述预处理的羰基铁粉的质量比为10～15:6～10:0.5～25。The method according to claim 1, wherein the mass ratio of the aqueous solution of cerium acetate, the mixed solution of butyl titanate acetate and the pretreated carbonyl iron powder is from 10 to 15:6 to 10:0.5. ~25.
  7. 根据权利要求1所述的方法，其特征在于，所述调节pH将pH值调节为3～5，在50～70℃的温度下加入所述乙酸，所述温度T为60～80℃。The method according to claim 1, wherein said adjusting the pH adjusts the pH to 3 to 5, and said acetic acid is added at a temperature of 50 to 70 ° C, said temperature T being 60 to 80 °C.
  8. 根据权利要求1所述的方法，其特征在于，所述搅拌的转速为600～800r/min；所述搅拌的时间为10～30min。The method according to claim 1, wherein the stirring speed is 600 to 800 r/min; and the stirring time is 10 to 30 minutes.
  9. 根据权利要求1所述的方法，其特征在于，所述煅烧的温度为800～900℃，所述煅烧的时间为1～3h。The method according to claim 1, wherein the calcination temperature is 800 to 900 ° C, and the calcination time is 1 to 3 h.
  10. 一种根据权利要求1-9中任一项所述的方法制备的吸波剂。A absorbing agent prepared by the method of any one of claims 1-9.
PCT/CN2018/083696 2017-12-26 2018-04-19 Wave-absorbing agent and preparation method therefor WO2019127991A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711433734.9A CN109957376A (en) 2017-12-26 2017-12-26 A kind of wave absorbing agent and preparation method thereof
CN201711433734.9 2017-12-26

Publications (1)

Publication Number Publication Date
WO2019127991A1 true WO2019127991A1 (en) 2019-07-04

Family

ID=67022231

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/083696 WO2019127991A1 (en) 2017-12-26 2018-04-19 Wave-absorbing agent and preparation method therefor

Country Status (2)

Country Link
CN (1) CN109957376A (en)
WO (1) WO2019127991A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110713661A (en) * 2019-10-21 2020-01-21 北京环境特性研究所 Low-frequency P-band wave-absorbing material and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112366057B (en) * 2020-10-23 2023-06-30 浙江工业大学 Organic-inorganic hybrid nano titanate coated metal soft magnetic composite material and preparation method thereof
CN115483383A (en) * 2022-09-30 2022-12-16 陕西科技大学 Barium titanate coated ternary cathode material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199169A (en) * 2015-11-02 2015-12-30 浙江欧仁新材料有限公司 Wave absorbing material and preparation method thereof
CN107033842A (en) * 2017-05-16 2017-08-11 山东大学 A kind of NEW TYPE OF COMPOSITE wave absorbing agent, preparation method and applications
CN107142079A (en) * 2016-03-01 2017-09-08 中国人民解放军军械工程学院 S, C-band composite electromagnetic absorbing material a kind of preparation method
CN108219663A (en) * 2018-01-08 2018-06-29 重庆大学 Containing the hud typed electric-controlled intelligent wave-absorbing coating material for inhaling wave particle

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101985395A (en) * 2010-11-26 2011-03-16 天津师范大学 Method for preparing high dielectric constant barium titanate ceramic
CN104673184B (en) * 2013-12-03 2016-09-07 深圳光启创新技术有限公司 A kind of wave absorbing agent, preparation method and applications
CN103951419B (en) * 2014-05-20 2015-04-15 电子科技大学 Preparation method of cerium-doped barium strontium titanate powder
CN106220244A (en) * 2016-07-28 2016-12-14 武汉理工大学 One has electro-magnetic wave absorption loss function haydite and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199169A (en) * 2015-11-02 2015-12-30 浙江欧仁新材料有限公司 Wave absorbing material and preparation method thereof
CN107142079A (en) * 2016-03-01 2017-09-08 中国人民解放军军械工程学院 S, C-band composite electromagnetic absorbing material a kind of preparation method
CN107033842A (en) * 2017-05-16 2017-08-11 山东大学 A kind of NEW TYPE OF COMPOSITE wave absorbing agent, preparation method and applications
CN108219663A (en) * 2018-01-08 2018-06-29 重庆大学 Containing the hud typed electric-controlled intelligent wave-absorbing coating material for inhaling wave particle

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JING, HONGXIA ET AL.: "Preparation and Microwave Absorbing Properties of Fe(CO)5/BaTiO3 Composites", JOURNAL OF MATERIALS ENGINEERING, vol. 43, no. 7, 31 July 2015 (2015-07-31), pages 38 - 42 *
ZHOU, YINGYIN G ET AL.: "Current Research Status of Oxidation Resistance of Carbonyl Iron Powders", MATERIALS REVIEW A: REVIEW, vol. 32, no. 3, 31 March 2018 (2018-03-31), pages 749 - 754, XP055623293 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110713661A (en) * 2019-10-21 2020-01-21 北京环境特性研究所 Low-frequency P-band wave-absorbing material and preparation method thereof
CN110713661B (en) * 2019-10-21 2022-03-08 北京环境特性研究所 Low-frequency P-band wave-absorbing material and preparation method thereof

Also Published As

Publication number Publication date
CN109957376A (en) 2019-07-02

Similar Documents

Publication Publication Date Title
WO2019127991A1 (en) Wave-absorbing agent and preparation method therefor
CN111014712B (en) Co/MnO@C composite electromagnetic wave absorbing material and preparation method and application thereof
CN111892093B (en) Microwave absorbing material and preparation method thereof
CN109943018B (en) Wave absorbing agent, wave absorbing material and respective preparation method
CN112210345A (en) Method for improving performance of wave-absorbing material with spherical composite core-shell structure
CN114195197B (en) Magnetic porous carbon compound and preparation method and application thereof
CN109837061A (en) Modified metal powder wave absorbing agent and preparation method thereof
CN111748317B (en) Petal-shaped ferric oxide-based composite wave absorbing agent and preparation method thereof and wave absorbing material
CN112456562A (en) Ferrite-based composite material and preparation method and application thereof
CN104559920A (en) Nano-particle composite with double-shell microstructure and application of nano-particle composite
Motamedi et al. Synthesis and microwave absorption characteristics of BaFe12O19/BaTiO3/MWCNT/polypyrrole quaternary composite
CN114634208A (en) Oxide composite material and preparation method and application thereof
CN108219663B (en) Containing the hud typed electric-controlled intelligent wave-absorbing coating material for inhaling wave particle
CN110028930B (en) HalS-Fe3O4@ C composite material and preparation method and application thereof
CN110835447A (en) Ku waveband composite wave-absorbing material and preparation method thereof
CN203882760U (en) Composite magnetic thin film
KR102011343B1 (en) Metal oxide / polymer composite having electromagnetic wave shielding ability in GHz band and electromagnetic wave shielding material manufactured using the same
CN110947950B (en) Preparation method of graphene modified FeCo absorbent
CN115275637A (en) Preparation method of titanium dioxide coated cobalt micro-nano wave-absorbing material
CN115160652B (en) Magnetic nanocellulose-carbon composite aerogel and preparation method and application thereof
KR20210038102A (en) Multi-dimensional zinc oxide coated iron oxide and manufacturing method thereof
CN114276781B (en) MO@NC core-shell structure type nano wave-absorbing material and preparation method thereof
CN115505910B (en) Magnetic metal @ SiC wave-absorbing powder and preparation method thereof
CN114613564B (en) High-permeability ferrite magnetic material and preparation method thereof
CN111073596A (en) Wave absorbing agent and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18896837

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18896837

Country of ref document: EP

Kind code of ref document: A1