CN114030269A - Manufacturing method of graphene-filled honeycomb wicking wave stealth composite material - Google Patents
Manufacturing method of graphene-filled honeycomb wicking wave stealth composite material Download PDFInfo
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Abstract
The invention discloses a method for manufacturing a graphene-filled honeycomb wicking wave stealth composite material, which belongs to the technical field of composite material molding and comprises the following steps: manufacturing and cutting the skin in advance to a required size; bonding the honeycomb core material on a skin at normal temperature by using a special adhesive film, and filling graphene powder materials with different contents or different components into the core grids of the honeycomb core material; after filling, covering a special glue film on the upper surface of the honeycomb core material, then placing the cured composite fiberboard, assembling the cured composite fiberboard into an autoclave for curing, and finally forming the graphene filled honeycomb core wave-absorbing composite material. According to the invention, the graphene filled honeycomb wicking wave stealth composite material meeting various wave-absorbing frequency band requirements can be prepared by changing the structure of the honeycomb core material or the components and the content of the filled graphene material according to different wave-absorbing frequency band requirements.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a manufacturing method of a graphene-filled honeycomb wicking wave stealth composite material.
Background
Graphene is a monoatomic layer, six-ring honeycomb lattice structure composed of carbon atoms in sp2 hybridized orbitals. The special two-dimensional structure endows graphene with excellent strength, toughness, light transmittance, electric conductivity and thermal conductivity. In particular to the electrical property, the linear dirac-like function electronic state density distribution of the graphene near the fermi surface enables the graphene to become a zero band gap semiconductor material or a metalloid conductor. The carrier mobility of graphene at room temperature can reach 15000 cm 2/V.s, which is 10 times of that of silicon material and is more than 2 times of that of indium antimonide (InSb) which is known to have the highest carrier mobility. In addition, due to the excellent light transmission performance and the super-tough mechanical property of the graphene, the graphene has a huge application prospect in flexible electric connection, transparent electrodes, bendable touch screen films and wearable microelectronic equipment.
In recent years, the wave absorbing characteristics of graphene and derivatives thereof to radar waves have been widely recognized in the scientific and technological field and the engineering field. The wave-absorbing characteristic of the material is derived from the comprehensive effects of the porous structure, the ultra-large specific surface area, the electromagnetic property, the thermal property and the like of the material. Due to the ultra-large specific surface area, the chemical bonds exposed to a large amount of graphene are easier to attenuate electromagnetic waves due to polarization relaxation of outer electrons under the action of an electromagnetic field. In addition, the graphene prepared by a chemical method has a large number of defects and functional group residues, so that the conductivity of the graphene is reduced, and the defects and the functional groups can generate a localized state of a Fermi level, which are beneficial to absorption and attenuation of electromagnetic waves and provide a basis for application of the graphene in the field of wave absorption.
The wave absorbing mechanism proposed at present has the following aspects:
(1) the porous structure is easy to form impedance matching with air, and electromagnetic waves are introduced more;
(2) countless interfaces formed by the holes enable electromagnetic waves to be reflected and refracted for multiple times, and multiple attenuation is formed to consume the electromagnetic waves;
(3) the graphene sheet layer structure and countless folds on the surface of the graphene sheet layer structure can reflect electromagnetic waves in more directions and form mutual interference to consume the electromagnetic waves;
(4) the high conductivity of graphene creates more eddy current effects and heat losses.
Compared with the common ferrite wave absorbing agent, the graphene has the characteristics of light weight, stability and the like, and has potential application prospect in the field of wave absorbing materials. However, although graphene has a wave-absorbing property, pure graphene has relatively weak wave-absorbing ability, and the wave-absorbing property of graphene is usually improved by introducing defects or doping.
As early as 2011, hakuang and 621 performed a reduction reaction on graphene oxide by a chemical method to obtain graphene with surface defects, and the surface defects are more beneficial to absorption of electromagnetic waves.
The honeycomb sandwich structure is a common structure wave-absorbing structure and mainly has the following advantages: (1) due to the effect of the sandwich, the requirements of light weight, strength and rigidity of the structural part can be more comprehensively met; (2) in consideration of wave absorbing performance, the electromagnetic wave entering the structure from the surface wave-transmitting layer can be scattered and absorbed for multiple times through the sandwich structure, so that the sandwich structure can more easily realize the functions of transmission, absorption and dispersion of the electromagnetic wave in the structure.
Researchers at Beijing aerospace university adopt a structural wave-absorbing design method to combine a glass fiber panel and a honeycomb core impregnated with an absorbent. Experiments show that the skin thickness of the honeycomb and the height of the honeycomb core have great influence on the electromagnetic absorption of the honeycomb structure. Common molding methods of the composite honeycomb sandwich structure include co-curing, secondary bonding and the like. The co-curing technology can realize the integral forming of parts, thereby reducing the number of parts, the additional weight of a connecting transition area and the workload, further lightening the structural weight, improving the fatigue strength and reducing the cost. The honeycomb sandwich wave-absorbing composite material consists of a composite material panel with good wave permeability and a honeycomb core filled with loss media, and has double functions of bearing and hiding. Factors influencing the comprehensive electromagnetic performance of the honeycomb sandwich wave-absorbing structure mainly lose the types and the concentrations of media, the height of the honeycomb core, the size of a core grid and the electromagnetic matching relationship among a free space, a wave-transmitting skin and the wave-absorbing honeycomb core. Wherein the lossy medium, which can also be called absorbent, has the greatest influence on the absorption properties. At present, the most applied absorbents mainly comprise ferromagnetic absorbents, carbon black, graphite and the like, and some novel absorbents such as graphene, carbon nano tubes, conductive polymers, novel plasma absorbents and the like are gradually shifted from laboratories to practical engineering applications. The ferromagnetic absorbent has high resistivity, has both dielectric loss and magnetic loss, can be mixed with resin to prepare a wave-absorbing slurry to impregnate an incompletely cured honeycomb core, so that wave-absorbing media are tightly and uniformly distributed on the wall of the honeycomb core, the density of the cured honeycomb core is increased, the rigidity is enhanced, and the wave-absorbing honeycomb core with the structure and the electromagnetic property improved simultaneously is prepared.
In the prior art, a graphene-coated honeycomb core product is usually manufactured by a process scheme of coating a graphene slurry or sizing material on the surface of a honeycomb core to prepare a coating, and finally drying and post-treating the coating to form a graphene-coated honeycomb core composite material. However, the above solution mainly has the following disadvantages:
1. the technical process of the scheme is complex, is immature at present and is basically in a laboratory research stage;
2. the thickness of the graphene coating layer cannot be too thick, and a limited range exists, so that the performance regulation and control are also limited;
3. the graphene coating layer is easy to age, crack or deteriorate, so that the performance is weakened or even lost;
4. the surface coating and the adhesion performance of the graphene coating are poor, and the graphene coating is easy to fall off in a use environment;
5. according to the existing knowledge, the graphene coating wave-absorbing honeycomb core composite material is mainly concentrated in a low-frequency band of 2 GHz and below in the effective absorption of 2-18GHz radar waves, and has poor medium-frequency and high-frequency wave-absorbing properties.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a graphene-filled honeycomb core wicking wave stealth composite material and a manufacturing method thereof.
In order to achieve the above object, the technical solution of the present invention is as follows:
a manufacturing method of a graphene-filled honeycomb wicking wave stealth composite material is characterized by comprising the following steps:
manufacturing and cutting the skin in advance to a required size;
bonding the honeycomb core material on a skin at normal temperature by using a special adhesive film, and filling graphene powder materials with different contents or different components into the core grids of the honeycomb core material;
after filling, covering a special glue film on the upper surface of the honeycomb core material, then placing the cured composite fiberboard, assembling the cured composite fiberboard into an autoclave for curing, and finally forming the graphene filled honeycomb core wave-absorbing composite material.
When the graphene powder material is filled, a manual filling or machine filling mode can be adopted.
The honeycomb core material is aramid paper honeycomb, ferrite honeycomb or a hybrid honeycomb formed by superposing the aramid paper honeycomb and the ferrite honeycomb.
The graphene powder material is pure graphene powder or composite powder of graphene powder and magnetic particles.
The cured composite fiber board is a carbon fiber composite board, a glass fiber composite board or a quartz fiber board.
The aramid paper honeycomb is an NH aramid honeycomb.
The graphene powder material may be one or more of flocculent graphene, expanded graphene or conventional mechanically exfoliated graphene.
In summary, the invention has the following advantages:
1) the invention provides a graphene filled wave-absorbing stealth honeycomb composite material and a manufacturing technology thereof, the graphene filled wave-absorbing stealth honeycomb composite material is used for replacing the existing wave-absorbing honeycomb composite material, the weight can be greatly reduced, and meanwhile, the material avoids the defect that the traditional wave-absorbing material needs to be frequently replaced;
2) the manufacturing process provided by the invention is simple in technology, easy to control and capable of quickly forming industrial transformation; the process does not involve toxic and harmful operation;
3) the manufacturing process method does not involve the use of graphene slurry and a coating layer, so that the problems of aging, cracking and other related failures of the coating material can be effectively avoided;
4) the graphene powder material filled in the honeycomb core lattice can have various material components or formulas, and has wide adjustable range and wide performance regulation limitation.
Drawings
FIG. 1 is a schematic diagram of a blank honeycomb sample;
FIG. 2 is a graph comparing vertical reflectance curves for a blank honeycomb (with quartz fiber panels);
fig. 3 is a schematic diagram of a graphene-filled single-layer honeycomb sample;
FIG. 4 is a graph of vertical reflectivity of different graphene-filled single-layer honeycombs;
FIG. 5 is a graph of vertical reflectance for a single-layer iron honeycomb filled with different amounts of graphene;
FIG. 6 is a graph of vertical reflectance of graphene-filled single-layer aramid honeycomb with different contents;
fig. 7 is a schematic diagram of a hybrid graphene filled honeycomb sample;
FIG. 8 is a graph of the performance of the optimized multilayer hybrid wave-absorbing honeycomb sandwich.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The invention provides a graphene-filled honeycomb wicking wave stealth composite material and a manufacturing method thereof, and the graphene-filled honeycomb wicking wave stealth composite material comprises the following steps:
manufacturing and cutting the skin in advance to a required size; bonding the honeycomb core material on a skin at normal temperature by using a special adhesive film, and filling graphene powder materials with different contents or different components into the core grids of the honeycomb core material; after filling, covering a special glue film on the upper surface of the honeycomb core material, then placing the cured composite fiberboard, assembling the cured composite fiberboard into an autoclave for curing, and finally forming the graphene filled honeycomb core wave-absorbing composite material.
When the graphene powder material is filled, a manual filling or machine filling mode can be adopted. The honeycomb core material is aramid paper honeycomb, ferrite honeycomb or hybrid honeycomb formed by superposing the aramid paper honeycomb and the ferrite honeycomb. The graphene powder material is pure graphene powder or composite powder of graphene powder and magnetic particles. The cured composite fiber board is a carbon fiber composite board, a glass fiber composite board or a quartz fiber board. The aramid paper honeycomb can be NH aramid honeycomb. The graphene powder material may be one or more of flocculent graphene, expanded graphene or conventional mechanically exfoliated graphene.
The honeycomb core is prepared by adopting two processes of co-curing and secondary glue joint, the special glue film is used for stabilizing the two sides of the honeycomb core, and then the co-curing process is adopted to prepare the honeycomb core.
By the manufacturing method, the graphene filled honeycomb wicking wave stealth composite material meeting the requirements of various wave-absorbing frequency bands can be manufactured by changing the structure of the honeycomb core material or the components and the content of the filled graphene material according to the requirements of different wave-absorbing frequency bands.
The use of the present invention is further illustrated by the following comparative experimental tests.
Testing one: (blank) single honeycomb core performance characterization, with reference to figure 1, the material parameters and test results are as follows:
materials: dimension and thickness of ferrite honeycomb sample: 200X 20 mm, 200 kg/m3The core grid size is 2.75; size and thickness of aramid fiber honeycomb sample: 200X 20 mm, 64 kg/m3The core size was 2.75.
The effective wave absorption loss is below-10 dB, and referring to the attached figure 2, the results show that the two types of iron honeycombs cannot effectively absorb waves in a low-frequency band S wave band and can effectively absorb waves in other three frequency bands, wherein the maximum wave absorption intensity appears in an X wave band, and the wave absorption intensity of the SKUF iron honeycombs is higher. In contrast, a single aramid honeycomb does not have wave-absorbing properties.
And (2) testing: in the filling test of different graphene powder types, referring to fig. 3, the material parameters and the test results are as follows:
materials: three different graphene powder materials fill the size and thickness of the iron honeycomb: 200X 20 mm, 8X 10 in volume-4 m3Density of 200 kg/m3160 g, core size 2.75. The experimental results were as follows (iron honeycomb, 30% content graphene 96 × 0.3 = 28.8 g):
referring to fig. 4, the result shows that the expanded graphite can realize 2.5-18GHz frequency band absorption, and the conventional graphene and the flocculent graphene cannot realize 4-6GHz radar wave absorption. Meanwhile, the wave absorbing strength of the flocculent graphene in each frequency band is relatively low.
And (3) testing: in the test of filling iron honeycomb with graphene powder with different contents, the material parameters and the test results are as follows:
materials: the iron honeycomb performance contrast of different graphite alkene filling content, iron honeycomb sample size thickness: 200X 20 mm, 200 kg/m3The size of the core lattice is 2.75, and the total weight of the pioneer graphite micro-tablets is as follows:
referring to the attached figure 5, the result shows that the whole wave-absorbing strength of the iron honeycomb is reduced due to the addition of the graphene, but when the content of the graphene reaches 50%, the wave-absorbing strength can be almost widened to a full radar frequency band, and the wave-absorbing performance can be reduced due to the fact that the content of the graphene is continuously increased.
And (4) testing: in the experiment of filling aramid paper honeycombs with graphene powder with different contents, the material parameters and the test results are as follows:
materials: the size and thickness of the filled aramid fiber honeycomb are 200 multiplied by 20 mm, NH-1-2.75-64, the performances of different contents of the aramid fiber honeycomb and graphene are verified, and the total weight of the filled pioneer graphite micro-sheet is as follows:
referring to the attached figure 6, the result shows that the addition of the graphene improves the overall wave-absorbing performance of the aramid fiber honeycomb, and when the content is 30%, the aramid fiber honeycomb has better absorption in a C frequency band and a part of X frequency bands; when the content is 100%, the absorption is better at S, X, Ku wave band.
And testing: the graphene filled hybrid honeycomb test has the following material parameters and test results:
materials: the sizes and thicknesses of the filled honeycombs of the serial numbers 1 to 4 are all as follows: 200X 20 mm, 8X 10 in volume-4 m3Density of 200 kg/m3160 g, core size 2.75. The first layer of the incident surface is verified by the hybrid wave-absorbing honeycomb of the aramid fiber honeycomb, and the configuration of each sample is shown in figure 7:
it can be seen from the results that, as shown in fig. 8, the hybrid honeycomb can meet the requirement that the reflectivity is less than-10 dB at 4-18GHz, has better wave-absorbing performance, and basically achieves the expected target.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. A manufacturing method of a graphene-filled honeycomb wicking wave stealth composite material is characterized by comprising the following steps:
manufacturing and cutting the skin in advance to a required size;
bonding the honeycomb core material on a skin at normal temperature by using a special adhesive film, and filling graphene powder materials with different contents or different components into the core grids of the honeycomb core material;
after filling, covering a special glue film on the upper surface of the honeycomb core material, then placing the cured composite fiberboard, assembling the cured composite fiberboard into an autoclave for curing, and finally forming the graphene filled honeycomb core wave-absorbing composite material.
2. The method for manufacturing the graphene-filled honeycomb wicking wave stealth composite material according to claim 1, wherein a manual filling or machine filling mode can be adopted when filling the graphene powder material.
3. The manufacturing method of the graphene-filled honeycomb wicking wave stealth composite material according to claim 1, wherein the honeycomb core material is an aramid paper honeycomb, a ferrite honeycomb or a hybrid honeycomb obtained by superposing the aramid paper honeycomb and the ferrite honeycomb.
4. The method for manufacturing the graphene-filled honeycomb wicking wave stealth composite material according to claim 1, wherein the graphene powder material is pure graphene powder or composite powder of graphene powder and magnetic particles.
5. The method of claim 1, wherein the cured composite fiber board is a carbon fiber composite board, a glass fiber composite board or a quartz fiber board.
6. The manufacturing method of the graphene-filled honeycomb wicking wave stealth composite material according to claim 3, characterized in that the aramid paper honeycomb is an NH aramid honeycomb.
7. The method for manufacturing the graphene-filled honeycomb wicking wave stealth composite material according to claim 1, wherein the graphene powder material may be one or more of flocculent graphene, expanded graphene or conventional mechanically exfoliated graphene.
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