CN115275637A - Preparation method of titanium dioxide coated cobalt micro-nano wave-absorbing material - Google Patents
Preparation method of titanium dioxide coated cobalt micro-nano wave-absorbing material Download PDFInfo
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Abstract
A preparation method of a titanium dioxide coated cobalt micro-nano wave-absorbing material relates to a preparation method of a wave-absorbing material, wherein the wave-absorbing material comprises magnetic metal Co micro-nano particles and an anatase type titanium dioxide layer, the Co micro-nano particles are an internal core, and the surface of the Co micro-nano particles is uniformly coated with a titanium dioxide shell layer. The method adopts a liquid phase reduction method and a sol-gel method to prepare Co @ TiO2The composite micro-nano particles have simple synthesis process, and the obtained Co @ TiO2The average diameter of the composite micro-nano particles is 0.5-3.5 mu m. In the field of electromagnetic wave absorption, co @ TiO2The composite micro-nano particles are used as a wave absorbing agent, the thickness of a wave absorbing body is 2.0-3.5 mm, the effective wave absorbing bandwidth is 5.9-18 GHz, and the wave absorbing agent can completely cover 50 percent of C, the whole X and Ku wave bands. The wave absorbing agent has simple process, low cost and good industrial application prospect.
Description
Technical Field
The invention relates to a preparation method of a wave-absorbing material, in particular to a preparation method of a titanium dioxide-coated cobalt micro-nano wave-absorbing material.
Background
With the rapid development of modern telecommunication technology, especially the arrival of 5G wireless communication technology, the production and the life of human beings are more and more convenient, and meanwhile, the electromagnetic radiation pollution is increasingly serious, so that the normal operation of electronic equipment is interfered, the public health is directly influenced, and the human health is harmed. Therefore, it is important to develop a high-performance wave-absorbing material with strong absorption capacity, wide frequency band, thin thickness and light weight. Ferromagnetic metal and alloy particles thereof have single loss mechanism (magnetic loss) and poor impedance matching, so that the performance is poor, and the requirements of thinness, lightness, width and strength cannot be met. In addition, the disadvantages of high density and poor chemical stability limit their practical applications. The dielectric material is introduced into the ferromagnetic metal particles to form the ferromagnetic/dielectric composite material, so that the electromagnetic property can be effectively adjusted, and the ferromagnetic/dielectric composite material has important scientific significance and application prospect on construction and wave-absorbing performance optimization of a novel wave-absorbing material.
Titanium dioxide (TiO)2) As a typical semiconductor material, the composite material has excellent dielectric loss capability, can effectively adjust the dielectric property of the material, and improves the electromagnetic attenuation capability of the composite material. Mixing TiO with2The composite material can improve the electromagnetic wave absorption performance of the material on the basis of obviously reducing the density of the material and improving the stability of the material. At the same time, tiO2A large number of defective dipoles and heterogeneous interfaces can be introduced, and the transition layer is used for reducing electromagnetic wave reflection and optimizing impedance matching. Che ren Tao et al, by introducing magnetic iron particles and dielectric TiO2The impedance matching of the layer is gradually improved, when the matching thickness is 2.0 mm, the maximum reflection loss is as high as 60.98 dB, and the absorption bandwidth is 4.8 GHz. Liutong et al prepared yolk shell structure Co @ SiO2The strongest reflection loss of the @ Void @ C nano composite material at 8.8 GHz reaches 44.5 dB; when the matching thickness is only 1.7 mm, the effective absorption bandwidth reaches 8.0 GHz (9.7 to 17.7 GHz). However, these synthesis methods are harsh, complex and time-consuming, and seriously hinder the practical application of ferromagnetic metal alloy particles. Meanwhile, the defects of low wave-absorbing efficiency and narrow bandwidth are in urgent need of improvement.
Disclosure of Invention
The invention aims to provide a preparation method of a cobalt-coated titanium dioxide micro-nano wave-absorbing material, and the invention relates to a method for controllably growing TiO on the surface of Co micro-nano particles by adopting a liquid-phase reduction method and a sol-gel method2The method of the core-shell structure wave-absorbing material of the layer improves dielectric relaxation and optimizes impedance matching in cooperation with strong magnetic loss, thereby enhancing wave-absorbing efficiency.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a titanium dioxide-coated cobalt micro-nano wave-absorbing material comprises the following preparation steps:
step one, preparing Co micro-nanospheres by a liquid phase reduction method:
step 1) dissolving cobalt chloride hexahydrate in ethylene glycol through water bath treatment at 85 ℃; adding sodium hydroxide and stirring for 20 min to obtain a mixed solution;
step 2), dropwise adding a hydrazine hydrate solution, and carrying out constant-temperature water bath at 85 ℃ for 1h to obtain metal cobalt particles;
step 3) repeatedly washing the cobalt particles by using deionized water and absolute ethyl alcohol to obtain pure cobalt particles;
step 4), putting the pure cobalt particles into a vacuum drying oven at 60 ℃ for drying treatment for 12 hours to prepare cobalt micro-nano particles;
step two, preparing Co @ TiO by sol-gel method2Compounding micro-nano particles:
step 1) dispersing Co micro-nano particles in a mixed solution of absolute ethyl alcohol and acetonitrile through ultrasonic treatment, and dropwise adding an ammonia water solution;
step 2) adding titanium source tetrabutyl titanate into the mixed solution and continuously stirring for 2h to obtain Co @ TiO2Core-shell structured particles;
step 3) using acetonitrile and absolute ethyl alcohol to Co @ TiO2The particles were washed repeatedly to obtain pure Co @ TiO2Particles;
step 4) reacting Co @ TiO2Drying the granules in a vacuum drying oven at 60 deg.C for 12h to obtain Co @ TiO2Micro-nano particles;
step 5) reacting Co @ TiO2Micro-nano particles in H2Calcining in a horizontal tube furnace at 500 ℃ for 2h under atmosphere to prepare anatase TiO2Coated Co micro-nano particles.
The preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material comprises magnetic metal Co micro-nano particles and an anatase type titanium dioxide layer, wherein the Co micro-nano particles are an inner core, and a titanium dioxide shell layer is uniformly coated on the surface of the Co micro-nano particles.
According to the preparation method of the titanium dioxide coated cobalt micro-nano wave-absorbing material, the size of the micro-nano particles is 0.5-3.5 mu m.
According to the preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material, the ratio of the volume of ethylene glycol to the amount of cobalt chloride hexahydrate is 1L.
According to the preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material, the mass ratio of sodium hydroxide to cobalt chloride hexahydrate is 6.5.
According to the preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material, the ratio of the volume of hydrazine hydrate to the amount of cobalt chloride hexahydrate is 750L.
According to the preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material, the volume ratio of absolute ethyl alcohol to acetonitrile is 3.
According to the preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material, the volume ratio of the mass of Co particles to titanium source tetrabutyl titanate is 0.5g.
According to the preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material, the volume ratio of the ammonia water to the titanium source tetrabutyl titanate is (2).
The preparation method of the titanium dioxide coated cobalt micro-nano wave-absorbing material is Co @ TiO2The composite micro-nano particles are used as a wave absorbing agent, the thickness of a wave absorbing body is 2.0-3.5 mm, the effective wave absorbing bandwidth is 5.9-18 GHz, and the coverage is 50 percent of C, the whole X and Ku wave bands.
The invention has the advantages and effects that:
the invention selects Co with higher Curie temperature as ferromagnetic metal core, and adopts sol-gel to prepare Co @ TiO2Micro-nano composite particles. Obtained Co @ TiO2The composite material has a typical core-shell structure, generates rich heterogeneous interfaces and enhances the interface polarization effect; a great amount of defects exist in the uniformly coated titanium dioxide shell layer, so that the dipole polarization effect is enhanced; the synergistic effect of the Co core and the titanium dioxide shell layer further improves the impedance matching, so that the obtained Co @ TiO2And excellent electromagnetic wave attenuation and loss are presented under the condition of thinner matching thickness. When the coating thickness is 2.3 mm, the maximum reflection loss reaches 56.6 dB, and the corresponding effective absorption bandwidth is 7.2 GHz (comprising 65% of Ku band and 82.5% of X band). The preparation method is simple, has low cost, and does not need complex equipment to be simultaneously supportedHas wide-band absorption of X and Ku wave bands, and is suitable for industrial mass production.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Step one, preparing Co micro-nanospheres by a liquid phase reduction method;
step 11, 0.02 mol of CoCl is treated by a water bath at 85 DEG C2·6H2Dissolving O in 200 mL of glycol; adding 0.13 mol of sodium hydroxide and stirring for 20 min to prepare a mixed solution;
step 12, dropwise adding 15 mL of hydrazine hydrate solution, and carrying out constant-temperature water bath at 85 ℃ for 1h to prepare metal cobalt particles;
step 13, centrifuging the product at the rotating speed of 3000 rpm for 5 min, removing supernatant, washing with distilled water for 5 times, and washing with absolute ethyl alcohol for 3 times to obtain pure cobalt particles;
and step 14, drying the pure cobalt particles in a vacuum drying oven at 60 ℃ for 12 hours to obtain the cobalt micro-nano particles.
Step two, preparing Co @ TiO by sol-gel method2Compounding micro-nano particles;
step 21, dispersing 0.5g of Co micro-nano particles in a mixed solution of 180 mL of absolute ethanol and 60 mL of acetonitrile through ultrasonic treatment, and dropwise adding 1mL of ammonia water solution;
step 22, adding 0.5 mL of titanium source tetrabutyl titanate into the mixed solution and continuously stirring for 2h to obtain Co @ TiO2Core-shell structured particles;
step 23, washing the obtained product with acetonitrile and absolute ethyl alcohol for 3 times respectively to obtain pure Co @ TiO2A particle;
step 24, adding Co @ TiO2Drying the granules in a vacuum drying oven at 60 deg.C for 12h to obtain Co @ TiO2Micro-nano particles;
step 25, co @ TiO2Micro-nano particles in H2Calcining in a horizontal tube furnace at 500 ℃ for 2h under the atmosphere to prepare anatase TiO2Coated Co micro-nano particles.
Example 2
Step one, preparing Co micro-nanospheres by a liquid phase reduction method;
step 11, 0.04 mol of CoCl is treated by a water bath at 85 DEG C2·6H2Dissolving O in 400 mL of glycol; adding 0.26 mol of sodium hydroxide and stirring for 20 min to prepare a mixed solution;
step 12, dropwise adding 30 mL of hydrazine hydrate solution, and carrying out constant-temperature water bath at 85 ℃ for 1h to prepare metal cobalt particles;
step 13, centrifuging the product at the rotating speed of 3000 rpm for 5 min, removing supernatant, washing with distilled water for 5 times, and washing with absolute ethyl alcohol for 3 times to obtain pure cobalt particles;
and step 14, drying the pure cobalt particles in a vacuum drying oven at 60 ℃ for 12 hours to obtain the cobalt micro-nano particles.
Step two, preparing Co @ TiO by sol-gel method2Compounding micro-nano particles;
step 21, dispersing 0.5g of Co micro-nano particles in a mixed solution of 180 mL of absolute ethanol and 60 mL of acetonitrile through ultrasonic treatment, and dropwise adding 1mL of ammonia water solution;
step 22, adding 0.5 mL of titanium source tetrabutyl titanate into the mixed solution and continuously stirring for 2h to obtain Co @ TiO2Core-shell structured particles;
step 23, washing the obtained product with acetonitrile and absolute ethyl alcohol for 3 times respectively to obtain pure Co @ TiO2Particles;
step 24, adding Co @ TiO2Drying the granules in a vacuum drying oven at 60 deg.C for 12h to obtain Co @ TiO2Micro-nano particles;
step 25, adding Co @ TiO2Micro-nano particles in H2Calcining in a horizontal tube furnace at 500 ℃ for 2h under the atmosphere to prepare anatase TiO2Coated Co micro-nano particles.
Example 3
Step one, preparing Co micro-nanospheres by a liquid phase reduction method;
step 11, 0.02 mol of CoCl is treated by a water bath at 85 DEG C2·6H2Dissolving O in 200 mL of glycol; adding 0.13 mol of sodium hydroxide and stirring for 20 min to prepare a mixed solution;
step 12, dropwise adding 15 mL of hydrazine hydrate solution, and carrying out constant-temperature water bath at 85 ℃ for 1h to obtain metal cobalt particles;
step 13, centrifuging the product at the rotating speed of 3000 rpm for 5 min, removing supernatant, washing with distilled water for 5 times, and washing with absolute ethyl alcohol for 3 times to obtain pure cobalt particles;
and step 14, placing the pure cobalt particles in a vacuum drying oven at 60 ℃ for drying treatment for 12 hours to obtain the cobalt micro-nano particles.
Step two, preparing Co @ TiO by sol-gel method2Compounding micro-nano particles;
step 21, dispersing 1.0 g of Co micro-nano particles in a mixed solution of 360 mL of absolute ethanol and 120 mL of acetonitrile through ultrasonic treatment, and dropwise adding 2 mL of ammonia water solution;
step 22, adding 1.0 mL of titanium source tetrabutyl titanate into the mixed solution and continuously stirring for 2h to obtain Co @ TiO2Core-shell structured particles;
step 23, washing the obtained product with acetonitrile and absolute ethyl alcohol respectively for 3 times to obtain pure Co @ TiO2A particle;
step 24, adding Co @ TiO2Drying the granules in a vacuum drying oven at 60 deg.C for 12h to obtain Co @ TiO2Micro-nano particles;
step 25, co @ TiO2Micro-nano particles in H2Calcining in a horizontal tube furnace at 500 ℃ for 2h under the atmosphere to prepare anatase TiO2Coated Co micro-nano particles.
Claims (10)
1. A preparation method of a titanium dioxide-coated cobalt micro-nano wave-absorbing material is characterized by comprising the following preparation steps:
step one, preparing Co micro-nanospheres by a liquid phase reduction method:
step 1) dissolving cobalt chloride hexahydrate in ethylene glycol through water bath treatment at 85 ℃; adding sodium hydroxide and stirring for 20 min to obtain mixed solution;
step 2), dropwise adding a hydrazine hydrate solution, and carrying out constant-temperature water bath at 85 ℃ for 1h to obtain metal cobalt particles;
step 3) repeatedly washing the cobalt particles by using deionized water and absolute ethyl alcohol to obtain pure cobalt particles;
step 4), putting the pure cobalt particles into a vacuum drying oven at 60 ℃ for drying treatment for 12 hours to prepare cobalt micro-nano particles;
step two, preparing Co @ TiO by sol-gel method2Composite micro-nano particles:
step 1) dispersing Co micro-nano particles in a mixed solution of absolute ethyl alcohol and acetonitrile through ultrasonic treatment, and dropwise adding an ammonia water solution;
step 2) adding titanium source tetrabutyl titanate into the mixed solution and continuously stirring for 2h to obtain Co @ TiO2Core-shell structured particles;
step 3) using acetonitrile and absolute ethyl alcohol to react with Co @ TiO2The particles were washed repeatedly to obtain pure Co @ TiO2Particles;
step 4) preparation of Co @ TiO2Drying the granules in a vacuum drying oven at 60 deg.C for 12h to obtain Co @ TiO2Micro-nano particles;
step 5) Co @ TiO2Micro-nano particles in H2Calcining in a horizontal tube furnace at 500 ℃ for 2h under the atmosphere to prepare anatase TiO2Coated Co micro-nano particles.
2. The preparation method of the cobalt-coated titanium dioxide micro-nano wave-absorbing material as claimed in claim 1, wherein the wave-absorbing material comprises magnetic Co micro-nano particles and an anatase type titanium dioxide layer, the Co micro-nano particles are an inner core, and a titanium dioxide shell layer is uniformly coated on the surface of the Co micro-nano particles.
3. The preparation method of the titanium dioxide coated cobalt micro-nano wave-absorbing material according to claim 1, wherein the size of the micro-nano particles is 0.5-3.5 μm.
4. The preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material according to claim 1, wherein the ratio of the volume of the glycol to the amount of cobalt chloride hexahydrate is 1L.
5. The preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material according to claim 1, wherein the mass ratio of the sodium hydroxide to the cobalt chloride hexahydrate is 6.5.
6. The preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material as claimed in claim 1, wherein the ratio of the volume of hydrazine hydrate to the amount of cobalt chloride hexahydrate is 750L.
7. The preparation method of the cobalt-coated titanium dioxide micro-nano wave-absorbing material according to claim 1, wherein the volume ratio of the absolute ethyl alcohol to the acetonitrile is 3.
8. The preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material according to claim 1, wherein the volume ratio of the mass of the Co particles to titanium source tetrabutyl titanate is 0.5g.
9. The preparation method of the titanium dioxide-coated cobalt micro-nano wave-absorbing material according to claim 1, wherein the volume ratio of the ammonia water to the titanium source tetrabutyl titanate is 2.
10. The method for preparing the cobalt-coated titanium dioxide micro-nano wave-absorbing material according to claim 1, wherein the Co @ TiO is used as the material2The composite micro-nano particles are used as a wave absorbing agent, the thickness of a wave absorbing body is 2.0-3.5 mm, the effective wave absorbing bandwidth is 5.9-18 GHz, and the coverage of 50 percent C, the whole X and Ku wave bands is realized.
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| CN116332162A (en) * | 2023-02-23 | 2023-06-27 | 之江实验室 | Honeycomb CNT/TiO 2 Composite material, preparation method and application thereof |
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