CN113708086A - Transition metal nano powder/carbon nano tube composite material and preparation method and application thereof - Google Patents
Transition metal nano powder/carbon nano tube composite material and preparation method and application thereof Download PDFInfo
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
- H01Q17/005—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems using woven or wound filaments; impregnated nets or clothes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a transition metal nano powder/carbon nano tube composite material and a preparation method and application thereof, belonging to the technical field of composite materials. The preparation method of the transition metal nano powder/carbon nano tube composite material comprises the following steps: and mixing and heating the carbon nano tube subjected to acidification treatment and the transition metal nano powder to obtain the transition metal nano powder/carbon nano tube composite material. The invention not only prepares the transition metal nano powder with extremely high purity, but also utilizes the transition metal nano powder to react with the carbon nano tube to ensure that the transition metal nano powder is evenly attached to the surface of the carbon nano tube to prepare the composite material with stable dielectric loss; and the cotton fabric is soaked in the composite material to prepare a fabric material with excellent wave absorption performance, thereby providing a research foundation for developing flexible wave absorption materials and stealth technology.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a transition metal nano powder/carbon nano tube composite material and a preparation method and application thereof.
Background
The wave-absorbing material plays an important role in the fields of radar stealth, aerospace, NFC (near field communication) antennas and the like. The radar stealth is realized by utilizing the appearance design, the realization difficulty is high and the cost is high due to the limitation of targets and forms, and the radar wave absorbing agent is generally adopted to achieve the purpose of stealth.
Nickel (Ni) is a hard and diffusive metal with strong ferromagnetism that can produce a high degree of polishing and corrosion resistance. The chemical property is more active but more stable. Nickel (Ni) is mainly used in conductive pigment materials made of paints, plastics, etc. to shield electromagnetic radiation interference and other materials. However, the density of the metal nickel is generally higher, the metal nickel can increase the overall quality when being coated as a wave-absorbing material, and the metal nickel has poor oxidation resistance in the application process and can be seriously oxidized at the temperature higher than 500 ℃, so that the metal nickel cannot be used on a large scale.
The carbon nano tube material is a novel one-dimensional flexible carbon atom nano material, and carbon atoms pass through sp2The hybrid compact combination can form a honeycomb crystal structure, has the characteristics of large length-diameter ratio, low density, large specific surface area, high conductivity, high mechanical strength and the like, shows good wave-absorbing characteristics from visible light to infrared wave frequency bands, but has small microwave permeability, thereby limiting the further improvement of the wave-absorbing performance of the carbon nano tube.
Based on the reasons, the transition metal nano powder/carbon nano tube composite material has great development significance for application of the transition metal and the carbon nano material in wave-absorbing materials, and the problems of high density and easy oxidation of the magnetic metal powder are solved while the microwave magnetic conductivity of the carbon nano tube is improved.
Disclosure of Invention
The invention aims to provide a transition metal nano powder/carbon nano tube composite material and a preparation method and application thereof, which aim to solve the problems in the prior art, and the transition metal nano powder/carbon nano tube composite material is obtained by mixing and heating acidified carbon nano tubes and transition metal nano powder, and a cotton fabric is soaked in a composite material solution to obtain a fabric with excellent wave absorption performance, thereby providing a good foundation for discovery of novel wave absorption materials and development of stealth technology.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: a preparation method of a transition metal nano powder/carbon nano tube composite material comprises the following steps: and mixing and heating the carbon nano tube subjected to acidification treatment and the transition metal nano powder to obtain the transition metal nano powder/carbon nano tube composite material.
Further, the acidification treatment specifically comprises: mixing the carbon nano tube with an acid solution in a ratio of 1-5 g: and (3) mixing 150-300 mL of the mixture, heating and refluxing the mixture at 100-120 ℃ for 8-16 h (if the solution is totally black and sticky, the carbon nano tube is completely acidified, and if the solution is not totally black and sticky, continuously refluxing the mixture until the solution is totally black and sticky), and washing and drying the mixture to obtain the acidified carbon nano tube.
Furthermore, when the solution becomes black and the solution is black viscous, the carbon nano tube is completely acidified; and if part of the solution is yellow (the yellow solution is an impurity solution containing nitrogen dioxide), separating the yellow solution, refluxing again until all the solution is black, standing for a period of time after refluxing, filtering with deionized water, finally washing the solution to be neutral, and drying for 24 hours to obtain the acidified carbon nano tube.
The purpose of the acidification treatment is to increase the activity of the carbon nanotubes (MWCNTs), perform a preliminary purification and remove impurities.
Further, the carbon nanotubes are multi-walled carbon nanotubes; the acid solution is a concentrated nitric acid solution with the mass fraction of 68-75%.
Further, the preparation of the transition metal nano powder specifically comprises: and mixing the transition metal salt solution with ethylene glycol, and then sequentially adding a sodium hydroxide solution, a sodium borohydride solution and a hydrazine hydrate solution to stir to obtain the transition metal nano powder.
Further, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 40%.
Further, the pH of the sodium borohydride solution is 14.
Sodium borohydride can be rapidly decomposed in neutral or acidic solution, and a small amount of ammonia water is added during preparation to prevent hydrolysis.
Still further, the mass fraction of the hydrazine hydrate solution is 20%.
Further, a small amount of NaOH solution in the hydrazine hydrate solution (hydrazine hydrate is very basic and NaOH solution is more easily added to regulate the reaction) forms a white paste-like consistency.
Further, the transition metal salt solution, ethylene glycol, sodium hydroxide solution, sodium borohydride solution and hydrazine hydrate solution are mixed in a volume ratio of 3: 2: 2: 2: 1, and mixing.
Further, the transition metal salt solution is a nickel sulfate solution.
Further, the carbon nano tube after the acidification treatment is further subjected to the following treatment before being mixed with the transition metal nano powder and heated: ultrasonic treatment is carried out in absolute ethyl alcohol solution, and then the solution is transferred into 2, 5-dihydroxy benzoic acid solution for ultrasonic treatment.
The second technical scheme of the invention is as follows: a transition metal nano powder/carbon nano tube composite material prepared by the preparation method of the transition metal nano powder/carbon nano tube composite material.
The third technical scheme of the invention is as follows: an application of transition metal nano powder/carbon nano tube composite material in preparing wave-absorbing material.
The fourth technical scheme of the invention is as follows: a preparation method of a wave-absorbing material comprises the following steps: preparing the transition metal nano powder/carbon nano tube composite material of claim 7 into a composite material aqueous solution, then soaking the pretreated cotton fabric in the composite material aqueous solution for padding treatment, and drying to obtain the wave-absorbing material.
Further, the pretreatment specifically comprises: soaking cotton fabrics with the size of 25cm multiplied by 25cm in alkali liquor with the mass of 50 times of that of the cotton fabrics, desizing the cotton fabrics in water bath at the temperature of 80-90 ℃ for 30min, washing the cotton fabrics with water and then boiling off the cotton fabrics.
Further, the pretreated alkali liquor is a sodium hydroxide solution, and the concentration of the alkali liquor is 10 g/L.
Furthermore, the scouring specifically comprises: boiling and boiling the cotton fabric in a sodium hydroxide solution with the concentration of 20g/L for 2 h.
The purpose of the pretreatment is to remove pectin, cottonseed hulls, grease, wax, nitrogenous substances, ash and other impurities attached to the cotton fabric during weaving, such as oil stains, PVA chemical and starch slurry which may be added during processing, and reduce the influence of the substances on the experimental results.
Further, the padding time is 30 min; the drying temperature is 60 ℃.
The invention discloses the following technical effects:
according to the invention, the carbon nano tube is subjected to acidification treatment, the transition metal nano powder is uniformly attached to the surface of the carbon nano tube, so that the transition metal nano powder/carbon nano tube composite material with extremely high purity is obtained, the transition metal nano powder/carbon nano tube composite material is not easy to oxidize when being applied at the temperature higher than 500 ℃, the transition metal is attached to the carbon nano tube, the weight of the wave-absorbing material is effectively reduced, and meanwhile, the magnetism of the transition metal is combined with the excellent conductivity of the carbon nano tube, so that the transition metal nano powder/carbon nano tube composite material has the properties of the transition metal and the carbon nano tube, the wave-absorbing property of the material is effectively improved, and the composite material with moderate conductivity, good stability, stable dielectric loss and lower magnetic loss is prepared.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart illustrating the preparation of a nickel/carbon nanotube composite material according to example 1 of the present invention;
FIG. 2 is an X-ray diffraction energy spectrum analysis diagram of the composite material and carbon nanotubes prepared in example 1 of the present invention, wherein CNTs are carbon nanotubes, and Ni-CNTs are nickel nanoparticle/carbon nanotube composite materials;
FIG. 3 is SEM images of the composite material and carbon nanotubes prepared in example 1 of the present invention, wherein a and b are SEM images of the nickel/carbon nanotube composite material, and c and d are SEM images of the carbon nanotube composite material;
FIG. 4 is an infrared spectrum analysis chart of the composite material and carbon nanotubes prepared in example 1 of the present invention, wherein CNTs are carbon nanotubes, and Ni-CNTs are nickel/carbon nanotube composite material;
FIG. 5 is a graph showing real and imaginary parts of the complex dielectric constant of the composite material and carbon nanotubes prepared in example 1 of the present invention, wherein Ni-CNTs ε 'is the real part of the complex dielectric constant of the nickel/carbon nanotube composite material, Ni-CNTs ε "is the imaginary part of the complex dielectric constant of the nickel/carbon nanotube composite material, CNTs ε' is the real part of the complex dielectric constant of the carbon nanotubes, and CNTs ε" is the imaginary part of the complex dielectric constant of the carbon nanotubes;
FIG. 6 is a graph showing the real and imaginary parts of the complex permeability of the composite material and carbon nanotube prepared in example 1 of the present invention, where Ni-CNTs μ 'is the real part of the complex permeability of the nickel/carbon nanotube composite material, Ni-CNTs μ' is the imaginary part of the complex permeability of the nickel/carbon nanotube composite material, CNTs μ 'is the real part of the complex permeability of the carbon nanotube, and CNTs μ' is the imaginary part of the complex permeability of the carbon nanotube;
FIG. 7 is a diagram of the dielectric loss tangent tan δ e of the composite material and carbon nanotubes prepared in example 1 of the present invention, wherein CNTs are carbon nanotubes, and Ni-CNTs are nickel/carbon nanotube composite materials;
FIG. 8 is a diagram of magnetic loss tangent tan δ m of the composite material and carbon nanotubes prepared in example 1 of the present invention, wherein CNTs are carbon nanotubes, and Ni-CNTs are nickel/carbon nanotube composite materials;
FIG. 9 is a wave-absorbing effect diagram of a Ku wave band of the composite material prepared in embodiments 2-6 of the invention;
FIG. 10 is a wave-absorbing effect diagram of X wave band of the composite material prepared in embodiments 2-6 of the invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
A preparation method of a transition metal/carbon nanotube composite material comprises the following steps:
(1) 150mL of concentrated nitric acid solution and 1g of multi-walled carbon nano-tubes are added into a 500mL round-bottom flask, reflux treatment is carried out at 120 ℃, the heating is stopped when the reflux treatment is carried out until the solution is completely black and is black sticky, deionized water is used for filtering and washing the solution to be neutral after standing, and the solution is dried for 24 hours in an electric heating hot air drying oven to obtain the acidified carbon nano-tubes.
(2) Preparing nickel nano powder: adding 1g of nickel sulfate into 75mL of distilled water for dissolution, adding 50mL of ethylene glycol, 50mL of NaOH aqueous solution with the mass fraction of 10%, and 50mL of NaBH with the pH value of 14 and the mass fraction of 5%4Aqueous solution (NaBH)4Aqueous solution with addition of small amount of ammonia to prevent hydrolysis of nitric acid), 25ml N2H4Solution (N)2H4Adding a small amount of NaOH aqueous solution into the solution to form a white pasty sticky matter), uniformly mixing, stirring at high speed (more finely and finely) by adopting ultrasound under the working condition of room temperature and humidity to prepare nickel nano powder (namely nickel nano particles) with the shape of the chain spherical nano particle crystal, mixing and cleaning the nickel nano powder with a small amount of absolute ethyl alcohol for 3 times, drying under vacuum, and refrigerating.
(3) Preparing a nickel/carbon nanotube composite material: adding 0.05g of acidified carbon nano tube into 100mL of 75% ethanol solution, carrying out ultrasonic treatment for 1h, adding (50) mL of 2, 5-dihydroxybenzoic acid, carrying out ultrasonic treatment for 30min, adding (1) g of nickel nano powder, mixing, stirring, carrying out centrifugal machine treatment, repeatedly washing with deionized water, and then drying at 60 ℃ for 12h to obtain the nickel/carbon nano tube composite material, wherein the preparation process is shown in figure 1.
Example 2
A preparation method of the wave-absorbing material comprises the following steps:
(1) cotton fabric pretreatment: adding 200g of cotton fabric with the size of 25cm multiplied by 25cm into 10kg of sodium hydroxide solution with the concentration of 10g/L, desizing for 30min in 80-90 ℃ constant-temperature water bath, fully washing twice with 80-90 ℃ hot water, washing for 10min each time, then washing with 50-60 ℃ water, finally fully washing with cold water to be neutral, drying in the air, putting into 20g/L sodium hydroxide solution, heating to boil and keeping boiling for 2h, repeating the desizing step after boiling, and then hanging the pretreated cotton fabric in an oven with the temperature not higher than 60 ℃ for drying.
(2) Dissolving 1g of the nickel/carbon nanotube composite material prepared in the embodiment 1 in 199mL of deionized water to prepare a nickel/carbon nanotube composite material dispersion liquid with the mass fraction of 0.5%, soaking the pretreated cotton fabric in the nickel/carbon nanotube composite material dispersion liquid for 30min, repeating the steps for three times, and finally drying the cotton fabric in an oven at about 60 ℃ to obtain the wave-absorbing material.
Example 3
The difference from example 2 is that the mass fraction of the nickel/carbon nanotube composite dispersion in step (2) is 1%.
Example 4
The difference from example 2 is that the mass fraction of the nickel/carbon nanotube composite dispersion in step (2) was 3%.
Example 5
The difference from example 2 is that the mass fraction of the nickel/carbon nanotube composite dispersion in step (2) is 5%.
Example 6
The difference from example 2 is that the mass fraction of the nickel/carbon nanotube composite dispersion in step (2) was 7%.
Effect example 1
The carbon nanotubes and the nickel/carbon nanotube composite material prepared in example 1 were subjected to X-ray diffraction spectroscopy (XRD), respectively, and the internal structure, the molecular composition, and the like of the material were known by a JEM-2100 type transmission electron microscope (JEOL, japan). When the test is carried out, the adopted conditions are as follows: cu target, K α: 0.15406nm, tube voltage: 36kV, tube current: 30mA, the scanning speed is 2 degrees/min, and the scanning range is 10-80 degrees; the results are shown in FIG. 2.
As can be seen from fig. 2, the chemical composition and crystalline phase structure of the carbon nanotubes and the nickel/carbon nanotube composite material were analyzed by XRD. The diffraction peak of the (002) crystal face of the carbon and the diffraction peak of the (111) crystal face of the nickel can be observed, and compared with the diffraction peak of the pure carbon nano tube, the diffraction peak of the carbon nano tube in the composite material has the advantages of reduced intensity, narrow width and no impurity peak, which indicates that the purity of the nickel nano powder in the prepared composite material is higher.
Effect example 2
Respectively carrying out micro-topography analysis (SEM) on the carbon nano tube and the nickel/carbon nano tube composite material prepared in the embodiment 1, selecting an TESCAN VEGA3 tungsten filament optical scanning electron microscope of Tissun International trade (Shanghai, group) Limited company, preparing metal powder with relatively large particle size into a sample, placing the sample on a piece of conductive adhesive by using a small-sized clamping button, clamping the original sample on a sample tray by using the clamping conductive adhesive, blowing the powder sample by using an ear washing ball for several times to avoid falling off, checking whether a screw is screwed down, carrying out topography characterization on the sample, and obtaining a result shown in figure 3.
It can be seen from fig. 3 that the nickel particles are uniformly attached to the surface of the carbon nanotube, and it can be seen from the figure that the inner diameter size of the nickel ions is about 10nm, the nickel ions are liquefied in the heating process and fall on the surface of the carbon nanotube to form a layer of non-crystal surface on the surface of the carbon nanotube and form chemical bonds with the carbon nanotube, the crystal phase is good, and the two substances coexist in the composite system.
Effect example 3
The carbon nanotubes and the nickel/carbon nanotube composite material prepared in example 1 were subjected to infrared spectroscopy (FT-IR), respectively, and a fourier transform type short wave infrared spectrometer was selected, which mainly used a non-dispersive infrared spectrometer and used infrared spectroscopy to detect the radical composition of the composite material, the results of which are shown in fig. 4.
As can be seen in FIG. 4, at 3411cm-1The broad peak is the stretching vibration peak of-OH, which shows that the acidified carbon nano tube contains a large amount of hydroxyl groups, and the absorption peak is 2970cm-1，1630cm-1，1395cm-1，1064cm-1And vibration characteristic peaks of C-H, C ═ C, C-OH and C-O are shown. The infrared spectrum curve of the nickel/carbon nanotube composite material is 3411cm-1the-OH peak is slightly enhanced, which provides more-OH after coating the nickel nano-layer, except for possessing the characteristic absorption peak of the carbon nano-tube, at 1553cm-1，1260cm-1And a new absorption peak is shown, which respectively represent the absorption peak of bending vibration of-N-H and the absorption peak of stretching contraction vibration of-C-N. After the nickel nano particles are loaded on the surface of the carbon nano tube, the infrared spectrum curve of the carbon nano tube is approximately similar to that of the carbon nano tube, which shows that the nickel nano particles are loaded, the influence on the active group structure of the carbon nano tube is small, and the nickel/carbon nano tube composite material can be stably dispersed in the base oil.
Effect example 4
After the nickel/carbon nanotube composite material prepared in the embodiment 1 of the invention is uniformly mixed with paraffin wax according to the mass ratio of 7:3, the mixture is heated by an intelligent magnetic stirrer, meanwhile, sufficient stirring is needed, after uniform mixing, the mixture is poured into a specific mould (the mould is a coaxial ring with the inner diameter of 3.04mm and the outer diameter of 7 mm), after cooling and solidification, the coaxial ring is taken out of the mould, VNA is adopted to test epsilon 'in the frequency range of 2-18 GHz to represent a complex dielectric constant real part, and epsilon' represents a complex dielectric constant imaginary part and mu 'to represent a complex real part and mu' represents a complex magnetic conductivity imaginary part and a dielectric loss tangent (tan delta ise) And magnetic loss tangent (tan. delta.)m) Six indexes, and associated knowledge of transmission line theory, for the value of reflection loss (R)L) Fitting the index to determine the size of the index under different thickness conditions; the results of the electromagnetic wave absorption measurement are shown in FIGS. 5 to 8.
As can be seen from FIG. 5, at 2GHz to 18GHz, the maximum imaginary part can reach 120 and the maximum real part can reach 60. With the increasing of the testing frequency, the real part and the imaginary part of the complex dielectric constant of the carbon nano tube are reduced in a gradient manner on the whole, but the real part and the imaginary part fluctuate up and down, but the real part starts to gradually increase at about 16GHz, the imaginary part decreases from 120 at the beginning to 0 and then increases to 60, and the real part decreases from 20 at the beginning to-10 and then increases to 60; from the figure, the real part and the imaginary part of the complex dielectric constant of the carbon nanotube are large, which shows that the carbon nanotube can absorb more incident electromagnetic waves and can perform great loss attenuation on the electromagnetic waves, and the electric conductivity is strong but unstable; in the range of 2-18 GHz, the real part and the imaginary part of the complex dielectric constant of the nickel/carbon nanotube composite material are very stable and are all about 10 by measuring the parameters of electromagnetism, the real part and the imaginary part of the complex dielectric constant reach the peak value when the frequency is 12GHz, the integral trend of the real part and the imaginary part is consistent, the imaginary part is always lower than the real part, and the comparison shows that the stability and the mutual matching degree of the metal composite materials such as the nickel/carbon nanotube and the like are increased by adding the nickel nanoparticles into the nickel/carbon nanotube composite material.
As can be seen from FIG. 6, by testing that the real part and the imaginary part of the complex permeability of the carbon nanotube of the electromagnetic parameter fluctuate between 0 and 10, and obviously fluctuate within the range of 15 to 18GHz, the trends of the real part and the imaginary part are kept consistent, and at 17GHz, the real part and the imaginary part of the complex permeability reach the peak, which are respectively 8 and 4, which shows that the magnetism of the carbon nanotube gradually increases with the increase of the frequency, that the storage capacity of the carbon nanotube in the range of 15 to 18GHz increases and then decreases, and that the attenuation capacity of the carbon nanotube increases and then decreases. Through testing of electromagnetic parameters in the frequency range of 2-18 GHz, observation of the real part and the imaginary part of the complex permeability of the nickel/carbon nanotube can show that the real part is uniformly maintained at 1 with the increase of frequency, while the imaginary part is changed with small amplitude near 0 with the increase of frequency, which shows that the attenuation capacity of the nickel/carbon nanotube to electromagnetic waves is poor, and the trend of the real part and the trend of the imaginary part are consistent, and the test shows that the carbon nanotube has good magnetism in the range of 15-18 GHz.
As shown in fig. 7, it can be seen that the dielectric loss tangent (tan δ e) of the carbon nanotube increases with the frequency, the dielectric loss tangent increases first, then decreases, then increases and then decreases, two peaks appear in the whole frequency range, which are respectively within two frequency ranges of 2 to 6GHz and 14 to 18GHz, the highest dielectric loss tangent (tan δ e) can reach 4, which indicates that the carbon nanotube has a strong but unstable and ineffective dielectric loss, and the dielectric loss tangent (tan δ e) of the nickel/carbon nanotube composite material is steadily increased with the increase of the frequency, which indicates that the nickel/carbon nanotube composite material has a strong, stable and effective dielectric loss.
As can be seen from fig. 8, the magnetic loss tangent (tan δ m) of the carbon nanotube increases, decreases, increases and decreases in the range of the tested frequency interval, and particularly, in the range of 15GHz to 18GHz, the fluctuation of the magnetic loss tangent is large, but the magnetic loss tangent (tan δ m) does not change much on the whole, which indicates that the carbon nanotube has relatively unstable magnetic loss and has stronger magnetic loss at partial frequency. The magnetic loss tangent (tan δ m) of the nickel/carbon nanotube composite material fluctuates only in a small range within the testing frequency range of 2-18 GHz, and in general, the magnetic loss tangent (tan δ m) of the nickel/carbon nanotube composite material gradually decreases with the increase of the frequency, which indicates that the nickel/carbon nanotube composite material has relatively weak magnetic loss.
In summary, ε 'represents the real part of the complex permittivity, ε "represents the imaginary part of the complex permittivity, μ' represents the real part of the complex permeability, and μ" represents the imaginary part of the complex permeability and the dielectric loss tangent (tan δ)e) And magnetic loss tangent (tan. delta.)m) The six indexes can obtain that the conductivity of the carbon nano tube is too high to cause impedance mismatching, the conductivity in a proper range can be exactly obtained after the nickel nano particles are added, the angle also indicates that the composite material has good stability and stable dielectric loss, the carbon nano tube has good but unstable magnetism, and the composite material after the transition metal is attached to the carbon nano tube has very stable property and low magnetic loss.
Effect example 5
The wave-absorbing material prepared in the embodiment 2-6 is subjected to Ku wave-band and X wave-band wave-absorbing performance tests
It can be seen from fig. 9 that, when the nickel/carbon nanotube coated fabric with different mass fractions is subjected to Ku waveband wave-absorbing performance test, when the nickel/carbon nanotube coated fabric with the mass fraction of 0.5% has almost no wave-absorbing effect, because the content of the dispersion is too low, in the coating process, the dispersion is immersed in the fabric yarn and does not float on the surface, so that the fabric has almost no wave-absorbing effect, and as the concentration of the dispersion increases, the wave-absorbing effect of the coated fabric becomes better in turn, but as the frequency increases, the wave-absorbing effect of the fabric decreases, which indicates that the coated fabric is more suitable for the Ku frequency band downlink. We divide Ku wave band into upper and lower lines, and find that the wave-absorbing effect of the coating fabric with the mass fraction of 7% is best-8 dB and the absorption rate can reach 84.2% at 10.7-12.75GHz in the lower line, but the wave-absorbing effect is unstable, and the wave-absorbing effect tends to be linearly weakened along with the increase of frequency, while the wave-absorbing effect of the coating fabric with the mass fraction of 3% is better and stable at 12.75-18.1GHz in the upper line, and is always kept at about-5 dB and the absorption rate is 68.4%.
As can be seen from fig. 10, the X-band wave-absorbing performance test is performed on the nickel/carbon nanotube coated fabric with different mass fractions, and it can be seen from the figure that the coated fabric with the mass fractions of 0.5% and 1% has almost no wave-absorbing effect in the X-band, approximately about-2 dB, and the absorption rate is approximately 36.9%, and most of the wave-absorbing effect is lost in a reflection or transmission manner. The fabric reflectivity of the coated fabric with the mass fraction of 3% is gradually reduced along with the increase of the frequency, namely the fabric wave-absorbing effect is better and better, and when the frequency is 12.5GHz, the fabric reflectivity reaches-8 dB and the absorptivity is 84.2%. And the fabric reflectivity of the coating fabric with the mass fraction of 5 percent shows the trend of decreasing firstly and then increasing gradually along with the increase of the frequency, namely the wave absorbing effect of the fabric is gradually improved and then gradually deteriorated, and at the frequency of 10GHz, the fabric reflectivity reaches-10 dB and the absorptivity is 90 percent. And the reflectivity of the coating fabric with the mass fraction of 7% is increased in sequence along with the increase of the frequency, and the wave absorbing effect of the fabric is poorer and poorer.
According to the 2 figures, wave absorbing performance tests of Ku wave bands and X wave bands are carried out on various coating fabrics, and according to the comparison of the 10 groups of data, the wave absorbing effect of the coating fabrics with the mass fraction of 0.5 percent and 1 percent is not ideal all the time, the coating fabrics with the mass fraction of 3 percent are stable all the time in the Ku wave bands and the X wave bands, and the reflectivity fluctuates in the range of-5 dB to-4 dB all the time; the wave absorbing effect of the coating fabric with the mass fraction of 5% in the X wave band is better than that of the Ku wave band; the wave absorbing effect of the coating fabric with the mass fraction of 7% is optimal no matter in an X wave band or a Ku wave band, but the stability is poor, and the reflectivity is large in floating. But the mass fraction is the same, the wave absorbing effect of the X wave band is always better than that of the Ku wave band.
Through chemical treatment of the carbon nano tube, nickel nano particles are uniformly attached to the surface of the carbon nano tube, structural representation is carried out on the nickel/carbon nano tube composite material, and the electromagnetic parameters, reflectivity and other parameters of the nickel/carbon nano tube composite material are tested after the nickel/carbon nano tube composite material is coated with a cotton fabric, and the conclusion is as follows:
(1) the nickel/carbon nano tube composite material is uniformly adhered after chemical treatment, no nickel oxide impurity peak appears, and the functional group of the carbon nano tube loaded with the nickel nano particles is not changed, which indicates that the chemical reaction does not damage the chemical bond.
(2) The conductivity of the nickel/carbon nanotube composite material conforms to impedance matching, and the nickel/carbon nanotube composite material has stable dielectric loss.
(3) In an X wave band and a Ku wave band, along with the increase of mass fraction, the reflectivity of the fabric is lower, the wave absorbing effect is better, the most stable wave absorbing effect is the coating fabric with the mass fraction of 3%, the reflectivity is-5 dB, the absorptivity is 68.4%, the best wave absorbing effect is the coating fabric with the mass fraction of 7%, the reflectivity is-12 dB, the absorptivity is 93.7%, and when the mass fractions are the same, the wave absorbing effect of the X wave band is better than that of the Ku wave band.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of a transition metal nano powder/carbon nano tube composite material is characterized by comprising the following steps: and mixing and heating the carbon nano tube subjected to acidification treatment and the transition metal nano powder to obtain the transition metal nano powder/carbon nano tube composite material.
2. The method for preparing the transition metal nanopowder/carbon nanotube composite material of claim 1, wherein the acidification treatment specifically comprises: mixing the carbon nano tube with an acid solution in a ratio of 1-5 g: and mixing 150-300 mL of the mixture, heating and refluxing the mixture for 8-16 h at 100-120 ℃, and washing and drying the mixture to obtain the carbon nano tube subjected to acidizing.
3. The method of claim 2, wherein the carbon nanotubes are multiwalled carbon nanotubes; the acid solution is a concentrated nitric acid solution with the mass fraction of 68-75%.
4. The method of claim 1, wherein the transition metal nanopowder is prepared by: and mixing the transition metal salt solution with ethylene glycol, and then sequentially adding a sodium hydroxide solution, a sodium borohydride solution and a hydrazine hydrate solution to stir to obtain the transition metal nano powder.
5. The method of claim 4, wherein the transition metal salt solution is a nickel sulfate solution.
6. The method for preparing a transition metal/carbon nanotube composite material according to claim 1, wherein the carbon nanotubes subjected to the acidification treatment are further subjected to the following treatments before being mixed with the transition metal nanopowder and heated: ultrasonic treatment is carried out in absolute ethyl alcohol solution, and then the solution is transferred into 2, 5-dihydroxy benzoic acid solution for ultrasonic treatment.
7. A transition metal nanopowder/carbon nanotube composite material prepared by the method of preparation of a transition metal nanopowder/carbon nanotube composite material according to any one of claims 1 to 6.
8. An application of the transition metal nanopowder/carbon nanotube composite material of claim 7 in the preparation of wave-absorbing materials.
9. The preparation method of the wave-absorbing material is characterized by comprising the following steps: preparing the transition metal nano powder/carbon nano tube composite material of claim 7 into a composite material aqueous solution, then soaking the pretreated cotton fabric in the composite material aqueous solution for padding treatment, and drying to obtain the wave-absorbing material.
10. The method for preparing the wave-absorbing material according to claim 9, wherein the padding time is 30 min; the drying temperature is 60 ℃.
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