CN112938928A - Carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance and preparation method and application thereof - Google Patents
Carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance and preparation method and application thereof Download PDFInfo
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- CN112938928A CN112938928A CN202110153264.0A CN202110153264A CN112938928A CN 112938928 A CN112938928 A CN 112938928A CN 202110153264 A CN202110153264 A CN 202110153264A CN 112938928 A CN112938928 A CN 112938928A
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Abstract
The invention discloses a carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic property, which is composed of carbon materials, wherein the carbon materials form a spiral structure, and the spiral structure has chiral characteristics. The carbon material is prepared from pure cotton materials and the like through a carbonization process, the prepared carbon material has an abnormal ferromagnetic property, and the abnormal ferromagnetic property and the magnetic property of a helical structure act together to influence the gain or absorption effect of the carbon material on microwaves. The carbon matrix metamaterial is prepared by carbonizing at different temperatures respectively, and can have a negative dielectric constant imaginary part or a negative magnetic permeability imaginary part. The microwave gain effect can be realized in the 2-18GHz frequency band after carbonization at 400 ℃ and 600 ℃, the microwave absorption effect can be realized in the 2-18GHz frequency band after carbonization at 700 ℃ and 800 ℃, and the effect of both gain and absorption can be realized in the 2-18GHz frequency band after carbonization at 1000 ℃. And the prepared carbon matrix spiral chiral structure metamaterial has the characteristics of excellent corrosion resistance, high temperature resistance and visible light antireflection.
Description
Technical Field
The invention relates to a metamaterial, in particular to a carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance.
Background
Microwave technology is commonly used in modern society, especially in the fields of communication technology, radar detection and anti-detection, and aerospace, and the performance of materials applied in different fields on microwaves is different, such as antennas of communication equipment or radars, which need to gain microwaves to achieve better signal strength. In the field of communication, filters or other wave-absorbing materials need to absorb microwaves. The above applications require materials to achieve good impedance matching with free space, and in the microwave range, the materials need to have both permittivity and permeability to ensure this property. The ferromagnetic material has many applications in related fields due to the above conditions, such as traditional iron, cobalt, nickel, etc., but the ferromagnetic material is poor in specific environmental adaptability, such as rapid oxidation and failure in marine salt mist corrosion environment and high temperature environment. On the other hand, although the non-ferromagnetic material can adapt to a severe environment, the non-ferromagnetic material has no ferromagnetism, so that the impedance matching performance of the non-ferromagnetic material is poor, and the non-ferromagnetic material is difficult to be applied to the communication or detection field. Therefore, the development of new materials, which realize good microwave gain or absorption performance, and have good corrosion resistance, high temperature resistance, etc., has become an important requirement in the related art. And if the invisible visible light is used in the field of radar stealth, the visible light anti-reflection capability is also needed to realize the multi-band stealth function. The visible light antireflection effect can also be applied in the fields of reducing urban light pollution, solar heating or power generation and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a spiral chiral structure metamaterial which is novel in structure, ingenious in conception, simple and convenient to prepare and takes a carbon material as a matrix. The core of the method is to realize abnormal performance: the carbon material which is originally non-ferromagnetic has ferromagnetism, and becomes a metamaterial by constructing a spiral structure, and the magnetic property of the material is further regulated and controlled under the combined action of the carbon material and the spiral structure. The composite material can respectively realize the gain or absorption function of microwaves at different carbonization temperatures, has excellent corrosion resistance and high temperature resistance, and can be applied in extreme environments. The solar energy anti-reflection coating has the anti-reflection function of visible light, has the characteristic of compatibility of microwave and visible light frequency bands, and can be applied to the fields of reducing urban light pollution, solar heating or power generation, invisible visible light and the like.
The technical solution of the invention is as follows: a carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance is characterized in that: the material is composed of carbon materials, the linear carbon materials rotate along a linear long axis to form the metamaterial with a spiral structure, and the spiral structure has chiral characteristics and can be divided into a left-hand spiral and a right-hand spiral. The carbon material is prepared from pure cotton materials and the like through a carbonization process, and the prepared carbon material has abnormal ferromagnetic property. The specific carbonization process comprises the steps of placing a sample in a tubular furnace, heating for 1-4 hours in an air atmosphere at the heating temperature of 200-300 ℃, then heating to a corresponding temperature in an argon atmosphere for carbonization, wherein the specific carbonization temperature is 400-1000 ℃, and the pure cotton material with the spiral structure still keeps the original shape after carbonization, so that the carbon material also has the spiral structure. The carbon material has ferromagnetism, and after the ferromagnetism and the magnetic property of the spiral structure act together, the carbon material with the chiral structure prepared by carbonizing at different temperatures can have a negative dielectric constant imaginary part or a negative magnetic conductivity imaginary part and has a gain or absorption effect on microwaves. The carbon matrix spiral chiral sequence metamaterial prepared by carbonizing at 400 ℃ has a negative dielectric constant imaginary part, and the carbon matrix spiral chiral sequence metamaterial prepared by carbonizing at the temperature of more than 700 ℃ has a negative magnetic permeability imaginary part. And after carbonization at 400 ℃ and 600 ℃, the microwave gain effect can be realized in the 2-18GHz frequency band, after carbonization at 700 ℃ and 800 ℃, the microwave absorption effect can be realized in the 2-18GHz frequency band, and after carbonization at 1000 ℃, the effect of both gain and absorption can be realized in the 2-18GHz frequency band.
Further, in the above technical solution, as the carbonization temperature increases, the negative value of the imaginary part of the permeability of the helical chiral carbon material decreases.
Further, in the above technical solution, the carbon material may have an abnormal ferromagnetic property, and such a ferromagnetic property affects its gain or absorption effect for the microwave.
Further, in the technical scheme, the prepared helical chiral structure carbon material has excellent corrosion resistance, high temperature resistance and visible light antireflection effect.
Compared with the prior art, the invention has the following advantages:
the carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic property has the advantage that a carbon material without ferromagnetism has ferromagnetism for the first time, so that the application problems in the fields of communication technology, radar detection, anti-detection, aerospace and the like are solved. The carbon material has excellent corrosion resistance and high temperature resistance, can adapt to different extreme environments, but is difficult to apply in the fields because the carbon material does not have ferromagnetic performance theoretically. In the past, many researches have been carried out to apply carbon materials to the above fields, and the carbon materials are compounded with traditional ferromagnetic materials (iron, cobalt, nickel or alloys thereof, etc.), but the method cannot fundamentally solve the problem that the materials are suitable for severe environments. Therefore, by adjusting the carbonization temperature and forming the spiral chiral structure, on one hand, the carbon material has certain ferromagnetic property at a proper carbonization temperature, and after the carbon material has the spiral structure, the magnetic permeability of the material can be adjusted by the interaction of the spiral structure and electromagnetic waves, and the ferromagnetic property of the material and the magnetic property of the spiral structure act together, so that the carbon material can solve the problems.
Drawings
FIG. 1 is a scanning electron micrograph of a spiral chiral structure of a carbon matrix metamaterial.
Fig. 2 shows the results of hysteresis loop tests of carbon materials themselves (powdery carbon materials) obtained by carbonization at different temperatures.
FIG. 3 shows the dielectric constant and permeability test results of carbon matrix helical chiral structure metamaterials at different carbonization temperatures.
FIG. 4 shows microwave absorption and gain performance of a single-layer carbon matrix spiral chiral structure metamaterial at different carbonization temperatures.
Fig. 5 shows the magnetic loss tangent of the carbon material itself (powdered carbon material) and the carbon matrix helical chiral structure metamaterial at a carbonization temperature of 700 degrees celsius.
FIG. 6 shows microwave absorption performance of a four-layer carbon matrix helical chiral structure metamaterial at a carbonization temperature of 700 ℃.
Fig. 7 shows microwave absorption performance of carbon matrix helical chiral sequence metamaterials obtained at a carbonization temperature of 700 ℃ after 7 days of salt spray corrosion.
FIG. 8 is a thermogravimetric analysis curve of a carbon matrix helical chiral sequence metamaterial obtained at a carbonization temperature of 700 degrees Celsius.
Fig. 9 is a photograph showing the comparison of the carbon matrix helical chiral structure metamaterial obtained at the carbonization temperature of 700 degrees centigrade with the visible light antireflection of the conventional microwave absorbing coating under the strong visible light irradiation.
Detailed Description
The following description will explain embodiments of the present invention with reference to the accompanying drawings.
Example 1
As shown in fig. 1, 2, 3, 4, 5, 6, 7, 8, and 9: a carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance is shown in figure 1, which is a right-hand spiral chiral structure scanning electron microscope picture obtained through carbonization at different temperatures, and the carbonization process comprises the steps of putting a commercially available and general pure cotton fabric with a spiral structure into a tube furnace (manufactured by Synfertile crystal material technology Co., Ltd., model OTF-1200X-II), and firstly carrying out pre-oxidation under an air atmosphere, wherein the pre-oxidation temperature is 270 ℃ and the time is 3 hours. Then annealing for 1 hour in argon atmosphere for carbonization, wherein the annealing carbonization temperature is respectively 400 ℃, 600 ℃, 700 ℃, 800 ℃ and 1000 ℃, and after carbonization, the cotton fabric still keeps the original spiral structure, and the carbon material with the spiral structure is obtained (figure 1). Wherein the diameter of the section of each single carbon spiral line is about 10 mu m, and the helicity rotates about 2 pi (1 period) at each 500 mu m length. The cotton fabric was ground with a mortar and tested for its hysteresis loop (fig. 2), at which time the cotton fabric was ground to powder without containing the helix structure, and thus its hysteresis loop represents the intrinsic properties of the carbon material. It can be seen from fig. 2 that the obtained carbon material per se shows ferromagnetic characteristics at different temperatures, namely, has the characteristics of small coercive force and easy saturated magnetization, and the saturated magnetization is highest at 700 ℃, which is 1.00523emu/g, and the coercive force is 59.884 Oe.
Under the action of incident microwaves, the ferromagnetic property of the carbon material and the combined action of the spiral chiral structure still act on a magnetic field, as shown in fig. 3, as the carbonization temperature increases, the negative value of the imaginary part of the magnetic permeability of the carbon substrate spiral chiral structure metamaterial decreases, which shows that the spiral structure can have a regulation and control effect on the magnetic property when the microwaves are incident, so that the carbon material which is considered to have no ferromagnetic property by the tradition can realize the regulation and control of the magnetic property through the combined action of the regulation of the carbonization temperature and the spiral chiral structure. In addition, in FIG. 3, the imaginary part of the dielectric constant is negative at 400 ℃, the lowest value of-0.0746 appears at 11.71GHz, and the dielectric constant and the magnetic permeability of the natural material are generally positive values, so that the carbon matrix helical chiral sequence metamaterial prepared by the invention can also be applied to some new applications.
The ferromagnetic properties of the carbon material itself in fig. 2 also affect the gain or absorption properties of the spirally ordered carbon material to microwaves, and fig. 4 shows that the upper and lower surfaces of a single-layer carbon fabric are coated with a thin layer of urethane resin, and then the reflection loss in the 2-18GHz band is measured in a microwave dark room, and it can be seen that the material exhibits the gain properties to microwaves at 400 ℃ and 600 ℃ in the full band (the reflection loss is positive), the absorption properties at 700 ℃ and 800 ℃ (the reflection loss is negative), and the properties of both gain and absorption at 1000 ℃. The higher the saturation magnetization shown in fig. 2, the better the microwave absorption performance of the material, illustrating the role of ferromagnetic properties in carbon matrix helical chiral structure metamaterials, where the carbon material itself has the highest saturation magnetization at 700 ℃ and the best microwave absorption performance.
FIG. 5 shows the magnetic loss tangent of the powdered carbon material and the carbon matrix helical chiral structure metamaterial under the carbonization condition of 700 ℃, and it can be seen that the magnetic loss tangent of the carbon matrix helical chiral structure metamaterial appears to be negative at high frequency and is greatly different from the value of the carbon powder, indicating that the magnetic property of the helical chiral carbon material is the result of the interaction between the carbon material itself and the helical structure.
The microwave control effect can also be enhanced by multilayer overlapping of spiral-structure carbon materials, the carbon materials with the temperature of 700 ℃ are overlapped and arranged in an upper layer and a lower layer, gaps among the carbon materials are bonded by thin-layer polyurethane resin, and the measured reflection loss is shown in figure 6, and can reach-7 dB (the absorptivity is more than or equal to 80%) of the reflection loss within a frequency band of 10.48-18GHz and-10 dB (the absorptivity is more than or equal to 90%) of the reflection loss within a frequency band of 13.08-18 GHz. The carbon matrix spiral chiral structure metamaterial prepared by the invention can realize wider effective absorption bandwidth without the help of traditional ferromagnetic metal. And because of the advantages of the carbon material, the carbon material can be applied in different severe environments, when the four layers of the carbon matrix spiral chiral structure metamaterial carbonized at 700 ℃ are overlapped after being subjected to salt spray corrosion for 7 days, the tested reflection loss is shown in figure 7, and the numerical value is basically unchanged compared with that in figure 6, thereby proving the corrosion resistance of the carbon material. FIG. 8 shows the curve of the results of thermogravimetric analysis of the carbon matrix helical chiral structure metamaterial carbonized at 700 ℃, which is completely exposed to the air atmosphere for heating test, and shows that the mass loss of the carbon material just reaches 10% at 377 ℃, thus proving the high temperature resistance. FIG. 9 shows a comparison of the visible light anti-reflection performance of a piece of carbon matrix helical chiral structure metamaterial placed on a conventional resin-based coating. The lamp tube is adopted to emit a section of visible light which is continuous along the length direction, so that the resin-based coating can obviously reflect the visible light, and the reflected visible light is disconnected on the surface of the carbon material, namely, the reflected visible light is not reflected on the surface of the carbon material.
Claims (5)
1. A carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance is characterized in that: the metamaterial matrix is made of carbon materials, the linear carbon materials rotate along a long linear axis to form a spiral structure, the diameter of the section of each single carbon spiral line is adjustable between 10nm and 100 mu m, the spiral structure has a chiral characteristic and can be divided into a left-hand spiral and a right-hand spiral, and the helicity can be adjusted between 0.1 and 10 periods (2 pi) of rotation at the length of every 500 mu m; the carbon material has abnormal ferromagnetic property, the saturation magnetization of the carbon material is adjustable between 0.2 and 300emu/g, and the imaginary part value of the magnetic conductivity is adjustable between-3 and 3.
2. A carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance is characterized in that: the metamaterial is formed by interweaving linear carbon materials.
3. A method of preparing a metamaterial as claimed in claim 1 or 2, wherein: the carbon material is prepared from a pure cotton material with a spiral structure through a carbonization process, the specific carbonization process comprises the steps of placing a sample in a tubular furnace, heating for 1-4 hours in an air atmosphere at the heating temperature of 200-300 ℃, then heating to a corresponding temperature in an argon atmosphere for carbonization, the specific carbonization temperature is 400-1000 ℃, and the pure cotton material with the spiral structure still keeps the original shape after carbonization, so that the carbon material also has the spiral structure.
4. The method for preparing a metamaterial according to claim 1, wherein: the carbon material with the chiral structure prepared by carbonization at different temperatures can have a negative dielectric constant imaginary part or a negative magnetic conductivity imaginary part and has a gain or absorption effect on microwaves; the carbon matrix spiral chiral sequence metamaterial prepared by carbonization at 400 ℃ has a negative dielectric constant imaginary part, and the carbon matrix spiral chiral sequence metamaterial prepared by carbonization at the temperature of more than 700 ℃ has a negative magnetic permeability imaginary part; and after carbonization at 400 ℃ and 600 ℃, the microwave gain effect can be realized in the 2-18GHz frequency band, after carbonization at 700 ℃ and 800 ℃, the microwave absorption effect can be realized in the 2-18GHz frequency band, and after carbonization at 1000 ℃, the effect of both gain and absorption can be realized in the 2-18GHz frequency band.
5. The metamaterial according to claim 1, wherein the metamaterial is applied to the fields of communication, radar and visible light stealth, solar heating and power generation.
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