CN113479940A - Carbon nanotube and carbonyl iron self-assembly wave absorbing agent and preparation method thereof - Google Patents

Carbon nanotube and carbonyl iron self-assembly wave absorbing agent and preparation method thereof Download PDF

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CN113479940A
CN113479940A CN202110903162.6A CN202110903162A CN113479940A CN 113479940 A CN113479940 A CN 113479940A CN 202110903162 A CN202110903162 A CN 202110903162A CN 113479940 A CN113479940 A CN 113479940A
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carbonyl iron
nano tube
carbon nano
self
preparing
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李皓
董斌
费大壮
徐鑫
陈为蔚
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Nanjing Guanxu New Materials Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/16Carbonyls
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/168After-treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
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    • C01B32/174Derivatisation; Solubilisation; Dispersion in solvents
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Abstract

The invention discloses a carbon nano tube and carbonyl iron self-assembly wave absorbing agent and a preparation method thereof, wherein the carbon nano tube is treated by an anionic surfactant, so that the surface of the carbon nano tube is negatively charged; simultaneously treating carbonyl iron by using a cationic surfactant to enable the surface of the carbonyl iron to be positively charged; in an aqueous solution, the carbon nano tube with negative electricity and carbonyl iron with positive electricity are combined in an electrostatic self-assembly mode, and then the carbon nano tube and the carbonyl iron are prepared into the composite wave absorbing agent with the self-assembly of the carbon nano tube and the carbonyl iron after drying. The prepared composite wave absorbing agent has excellent electromagnetic wave absorption performance.

Description

Carbon nanotube and carbonyl iron self-assembly wave absorbing agent and preparation method thereof
Technical Field
The invention belongs to the field of materials, relates to a wave absorbing agent, and particularly relates to a carbon nano tube and carbonyl iron self-assembly wave absorbing agent and a preparation method thereof.
Background
With the development of social science and technology, electromagnetic waves are widely applied in the fields of communication, electrical appliances, military, medical treatment and the like, and people enjoy convenience in technological progress and are also inevitably influenced by electromagnetic wave radiation. Electromagnetic radiation can have adverse effects on the human body, and can firstly affect sensory nerve endings of the human body, thereby affecting the central nerve. Under the influence, organs such as hearts, pancreas and eyes of human bodies are easy to feel uncomfortable, and severe situations can cause palpitation, blood pressure reduction and even vision loss. Therefore, the electromagnetic wave absorbing material plays an important role in stealth technology and protection of human beings. The good wave-absorbing material is required to be thin in thickness, light in weight and excellent in electromagnetic wave absorption performance, wherein the effective absorption bandwidth is the most important index for evaluating the wave-absorbing performance of the wave-absorbing agent.
Carbonyl iron is a common typical magnetic metal wave-absorbing material and is obtained by decomposing iron pentacarbonyl, the raw material of the carbonyl iron is black powder, the particles of the carbonyl iron are spherical, the particle size of the carbonyl iron is 1-10 mu m, and the iron content of the material per se is more than 97%. In recent years, in many studies on carbonyl iron, in order to increase the width-thickness ratio and shape anisotropy thereof and achieve the purpose of breaking through the Snoek's limitation, researchers ball-mill the micro-morphology of the original carbonyl iron from a spherical shape into a flake shape. Carbonyl iron is a material which is earlier applied to the wave-absorbing field in magnetic metal, but along with the development of science and technology, the requirement on the effective absorption bandwidth of the carbonyl iron is higher and higher.
The carbon nano tube has light weight and high conductivity, and has been widely applied to the wave absorbing field as a dielectric loss type wave absorbing agent. However, when the carbon nanotube is used as a wave absorbing agent alone, the loss mechanism is still limited to the resistance type loss related to the conductivity, and the defects of poor impedance matching, weak absorption strength, narrow wave absorbing frequency band and the like still exist.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of a carbon nano tube and carbonyl iron self-assembly wave-absorbing agent, the carbon nano tube and the carbonyl iron are effectively combined together in an electrostatic self-assembly mode, and the finally prepared composite wave-absorbing agent has wider effective absorption bandwidth and wide application prospect in the wave-absorbing field
In order to achieve the above object, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which comprises the following steps: treating the carbon nano tube by using an anionic surfactant to make the surface of the carbon nano tube carry negative charges; simultaneously treating carbonyl iron by using a cationic surfactant to enable the surface of the carbonyl iron to be positively charged; in an aqueous solution, the carbon nano tube with negative electricity and carbonyl iron with positive electricity are combined in an electrostatic self-assembly mode, and then the carbon nano tube and the carbonyl iron are prepared into the composite wave absorbing agent with the self-assembly of the carbon nano tube and the carbonyl iron after drying.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: the method comprises the following steps:
step one, preparing a carbon nano tube with negative electricity: preparing an anionic surfactant aqueous solution; adding the carbon nano tube into an anionic surfactant aqueous solution, and carrying out ultrasonic treatment for 2-3 hours; filtering and drying to obtain the carbon nano tube with negative electricity;
step two, preparing sheet carbonyl iron with positive charges: preparing a cationic surfactant aqueous solution; adding carbonyl iron into a cationic surfactant aqueous solution, and carrying out ultrasonic treatment for 2-3 hours; carrying out suction filtration and drying to obtain positively charged carbonyl iron;
step three, preparing the carbon nano tube and carbonyl iron self-assembly composite wave absorbing agent: preparing a carbon nano tube with negative electricity and carbonyl iron with positive electricity into an aqueous solution; stirring for 30min, and standing the mixed solution for 30 min; and (4) carrying out suction filtration and drying to obtain the composite wave absorbing agent formed by self-assembling the carbon nano tube and the carbonyl iron.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the carbon nano tube is one or more of a single-wall carbon nano tube, a double-wall carbon nano tube and a multi-wall carbon nano tube.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the carbonyl iron is one or more of spherical carbonyl iron or flaky carbonyl iron.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the anionic surfactant is one or more of sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium alkyl polyoxyethylene ether sulfate and sodium fatty acid.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the cationic surfactant is one or more of cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride and dodecyl dimethyl amine oxide.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the concentration of the anionic surfactant aqueous solution is 0.05-20 g/L. The dosage ratio of the carbon nano tube to the anionic surfactant aqueous solution is 5 g: 500 mL.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the concentration of the cationic surfactant aqueous solution is 0.05-20 g/L. The dosage ratio of the carbonyl iron to the cationic surfactant aqueous solution is 5 g: 500 mL.
Further, the present invention provides a method for preparing a carbon nanotube and carbonyl iron self-assembled wave absorber, which may further have the following characteristics: wherein the mass ratio of the carbon nano tube with negative electricity to the carbonyl iron with positive electricity is 1:100-20: 100. The concentration of the aqueous solution of the negatively charged carbon nanotubes and the positively charged carbonyl iron was 1.1g/250 mL.
The invention also protects the carbon nano tube and carbonyl iron self-assembly wave absorbing agent prepared by the preparation method.
The invention has the beneficial effects that: the invention provides a carbon nano tube and carbonyl iron self-assembly wave absorbing agent and a preparation method thereof. The strong electrostatic combination is beneficial to generating interface polarization, thereby increasing the wave absorbing performance after compounding. The composite wave absorbing agent combines the advantages of two materials, has a double wave absorbing mechanism of dielectric loss and magnetic loss, has excellent electromagnetic wave absorption performance, and has wide application prospect in the field of electromagnetic wave absorption.
Drawings
FIG. 1 is a wave-absorbing performance diagram of the carbon nanotube and carbonyl iron self-assembled wave-absorbing agent of example 1;
FIG. 2 is a wave-absorbing property diagram of the mixed powder wave-absorbing agent of comparative example 1;
FIG. 3 is a wave-absorbing property diagram of carbonyl iron of comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a carbon nanotube and carbonyl iron self-assembly wave absorber, and the preparation method comprises the following steps:
step one, preparing a carbon nano tube with negative electricity:
500mL of sodium dodecyl benzene sulfonate aqueous solution with the concentration of 10g/L is prepared;
weighing 5g of carbon nano tube, adding the carbon nano tube into sodium dodecyl benzene sulfonate aqueous solution, and carrying out ultrasonic treatment for 2 hours;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in a 60 ℃ oven for 24 hours to obtain the carbon nano tube with negative charges.
Step two, preparing sheet carbonyl iron with positive charges:
500mL of hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 10g/L is prepared;
weighing 5g of sheet carbonyl iron, adding the sheet carbonyl iron into a hexadecyl trimethyl ammonium bromide aqueous solution, and carrying out ultrasonic treatment for 2 hours;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in an oven at 60 ℃ for 24h to obtain the sheet carbonyl iron with positive charges.
Step three, preparing the carbon nano tube and carbonyl iron self-assembly composite wave absorbing agent:
preparing a carbon nano tube with negative electricity and carbonyl iron with positive electricity into an aqueous solution;
weighing 0.1g of carbon nano tube with negative charge and 1g of sheet carbonyl iron with positive charge, and preparing into 250ml of aqueous solution;
stirring the solution at the speed of 50rpm for 30min, standing for 30min, and combining the carbon nano tube with negative charge and carbonyl iron with positive charge in an electrostatic self-assembly manner;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in a 60 ℃ oven for 24h to obtain the composite wave absorbing agent with the self-assembled carbon nano tube and carbonyl iron.
The composite wave absorbing agent and paraffin are pressed according to the mass ratio of 7:3, the wave absorbing performance is tested by using a coaxial method, when the thickness of the composite wave absorbing agent is 1.5mm, the effective absorption bandwidth within 2-18GHz is 9.5GHz (8.5-18 GHz), and the test chart of the wave absorbing performance is shown in figure 1, so that the ultra-wideband absorption under the ultra-thin thickness is realized.
Example 2
The embodiment provides a carbon nanotube and carbonyl iron self-assembly wave absorber, and the preparation method comprises the following steps:
step one, preparing a carbon nano tube with negative electricity:
500mL of alkyl sodium sulfate aqueous solution with the concentration of 0.05g/L is prepared;
weighing 5g of carbon nano tube, adding the carbon nano tube into an alkyl sodium sulfate aqueous solution, and carrying out ultrasonic treatment for 3 hours;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in a 60 ℃ oven for 24 hours to obtain the carbon nano tube with negative charges.
Step two, preparing sheet carbonyl iron with positive charges:
preparing 500mL of dodecyl dimethyl amine oxide aqueous solution with the concentration of 0.05 g/L;
weighing 5g of spherical carbonyl iron, adding the spherical carbonyl iron into a dodecyl dimethyl amine oxide aqueous solution, and carrying out ultrasonic treatment for 3 hours;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in an oven at 60 ℃ for 24h to obtain the sheet carbonyl iron with positive charges.
Step three, preparing the carbon nano tube and carbonyl iron self-assembly composite wave absorbing agent:
preparing a carbon nano tube with negative electricity and carbonyl iron with positive electricity into an aqueous solution;
weighing 0.1g of carbon nano tube with negative charge and 10g of sheet carbonyl iron with positive charge, and preparing into 250ml of aqueous solution;
stirring the solution at the speed of 50rpm for 30min, standing for 30min, and combining the carbon nano tube with negative charge and carbonyl iron with positive charge in an electrostatic self-assembly manner;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in a 60 ℃ oven for 24h to obtain the composite wave absorbing agent with the self-assembled carbon nano tube and carbonyl iron.
Example 3
The embodiment provides a carbon nanotube and carbonyl iron self-assembly wave absorber, and the preparation method comprises the following steps:
step one, preparing a carbon nano tube with negative electricity:
500mL of an alkyl polyoxyethylene ether sodium sulfate aqueous solution with the concentration of 20g/L is prepared;
weighing 5g of carbon nano tube, adding the carbon nano tube into an alkyl polyoxyethylene ether sodium sulfate aqueous solution, and carrying out ultrasonic treatment for 2.5 hours;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in a 60 ℃ oven for 24 hours to obtain the carbon nano tube with negative charges.
Step two, preparing sheet carbonyl iron with positive charges:
500mL of octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 20g/L is prepared;
weighing 5g of spherical carbonyl iron, adding the spherical carbonyl iron into an aqueous solution of octadecyl trimethyl ammonium chloride, and carrying out ultrasonic treatment for 2.5 hours;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in an oven at 60 ℃ for 24h to obtain the sheet carbonyl iron with positive charges.
Step three, preparing the carbon nano tube and carbonyl iron self-assembly composite wave absorbing agent:
preparing a carbon nano tube with negative electricity and carbonyl iron with positive electricity into an aqueous solution;
weighing 0.2g of carbon nano tube with negative charge and 1g of sheet carbonyl iron with positive charge, and preparing into 250ml of aqueous solution;
stirring the solution at the speed of 50rpm for 30min, standing for 30min, and combining the carbon nano tube with negative charge and carbonyl iron with positive charge in an electrostatic self-assembly manner;
and carrying out suction filtration treatment on the mixed solution, and drying the obtained paste in a 60 ℃ oven for 24h to obtain the composite wave absorbing agent with the self-assembled carbon nano tube and carbonyl iron.
Comparative example 1
This comparative example provides a mixed powder wave absorber, which is prepared by a method different from that of example 1: the carbon nano tube and the carbonyl iron are not modified and are simply and mechanically blended.
Specifically, the carbon nanotubes in example 1 and the sheet carbonyl iron were mechanically blended in a mass ratio of 1: 10.
The mixed powder wave absorbing agent and paraffin are pressed according to the mass ratio of 7:3, the wave absorbing performance is tested by using a coaxial method, the effective absorption bandwidth of the composite wave absorbing agent in 2-18GHz is only 7.5GHz (10.5-18 GHz) when the thickness of the composite wave absorbing agent is 1.5mm, the test graph of the wave absorbing performance is shown in figure 2, and the effective absorption bandwidth is greatly reduced compared with that of the composite wave absorbing agent in the embodiment 1.
Comparative example 2
According to the comparative example, carbonyl iron is used as a wave absorbing agent, a sheet carbonyl iron and paraffin are subjected to compression ring according to the mass ratio of 7:3, the wave absorbing performance is tested by using a coaxial method, the effective absorption bandwidth of the composite wave absorbing agent in the range of 2-18GHz is only 6.2GHz (9.1-15.3 GHz) when the thickness of the composite wave absorbing agent is 1.5mm, the test chart of the wave absorbing performance is shown in figure 3, and the effective absorption bandwidth is greatly reduced compared with that of the composite wave absorbing agent in example 1.
Comparing example 1 with comparative examples 1 and 2, it can be seen that the carbon nanotubes and carbonyl iron are effectively combined together by the electrostatic self-assembly method used in the invention, and a composite wave absorbing agent with self-assembled carbon nanotubes and carbonyl iron is prepared. After the composite wave absorbing agent is combined in the electrostatic self-assembly mode, the effective absorption bandwidth of the wave absorbing agent can be greatly improved, the ultra-wide-band absorption is really realized, and the wave absorbing agent has wide application prospect in the field of electromagnetic wave absorption. Meanwhile, the electrostatic self-assembly mode also provides a new idea for compounding the wave absorber and widening the effective absorption bandwidth, and has certain guiding significance for preparing the novel carbon material wave absorber.

Claims (10)

1. A preparation method of a carbon nano tube and carbonyl iron self-assembly wave absorbing agent is characterized by comprising the following steps:
treating the carbon nano tube by using an anionic surfactant to make the surface of the carbon nano tube carry negative charges; simultaneously treating carbonyl iron by using a cationic surfactant to enable the surface of the carbonyl iron to be positively charged;
in an aqueous solution, the carbon nano tube with negative electricity and carbonyl iron with positive electricity are combined in an electrostatic self-assembly mode, and then the carbon nano tube and the carbonyl iron are prepared into the composite wave absorbing agent with the self-assembly of the carbon nano tube and the carbonyl iron after drying.
2. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 1, wherein the method comprises the following steps:
the method comprises the following steps:
step one, preparing a carbon nano tube with negative electricity: preparing an anionic surfactant aqueous solution; adding the carbon nano tube into an anionic surfactant aqueous solution, and carrying out ultrasonic treatment for 2-3 hours; filtering and drying to obtain the carbon nano tube with negative electricity;
step two, preparing sheet carbonyl iron with positive charges: preparing a cationic surfactant aqueous solution; adding carbonyl iron into a cationic surfactant aqueous solution, and carrying out ultrasonic treatment for 2-3 hours; carrying out suction filtration and drying to obtain positively charged carbonyl iron;
step three, preparing the carbon nano tube and carbonyl iron self-assembly composite wave absorbing agent: preparing a carbon nano tube with negative electricity and carbonyl iron with positive electricity into an aqueous solution; stirring for 30min, and standing the mixed solution for 30 min; and (4) carrying out suction filtration and drying to obtain the composite wave absorbing agent formed by self-assembling the carbon nano tube and the carbonyl iron.
3. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 1, wherein the method comprises the following steps:
wherein the carbon nano tube is one or more of a single-wall carbon nano tube, a double-wall carbon nano tube and a multi-wall carbon nano tube.
4. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 1, wherein the method comprises the following steps:
wherein the carbonyl iron is one or more of spherical carbonyl iron or flaky carbonyl iron.
5. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 1, wherein the method comprises the following steps:
wherein the anionic surfactant is one or more of sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium alkyl polyoxyethylene ether sulfate and sodium fatty acid.
6. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 1, wherein the method comprises the following steps:
wherein the cationic surfactant is one or more of cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride and dodecyl dimethyl amine oxide.
7. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 2, wherein the method comprises the following steps:
wherein the concentration of the anionic surfactant aqueous solution is 0.05-20 g/L.
8. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 2, wherein the method comprises the following steps:
wherein the concentration of the cationic surfactant aqueous solution is 0.05-20 g/L.
9. The method for preparing the carbon nanotube and carbonyl iron self-assembly wave absorber according to claim 1, wherein the method comprises the following steps:
wherein the mass ratio of the carbon nano tube with negative electricity to the carbonyl iron with positive electricity is 1:100-20: 100.
10. The carbon nanotube and carbonyl iron self-assembly wave absorber prepared by the preparation method of any one of claims 1 to 9.
CN202110903162.6A 2021-08-06 2021-08-06 Carbon nanotube and carbonyl iron self-assembly wave absorbing agent and preparation method thereof Pending CN113479940A (en)

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