CN110713661B - Low-frequency P-band wave-absorbing material and preparation method thereof - Google Patents
Low-frequency P-band wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-frequency P-band wave-absorbing material and a preparation method thereof. The method comprises the following steps: modifying graphene powder by using a first surfactant to prepare a functionalized graphene dispersion liquid; compounding the functionalized graphene dispersion liquid with spherical magnetic alloy particles by a high-energy ball milling method to prepare a functionalized graphene/flaky magnetic alloy particle composite absorbent; coating the composite absorbent by using a second surfactant to prepare a low-frequency P-band absorbent; and mixing the low-frequency P-band absorbent with ethylene propylene diene monomer, and then carrying out rubber mixing and calendering processes to obtain the low-frequency P-band wave-absorbing material. The invention provides a new idea for expanding the low-frequency P-band wave-absorbing material, the effective absorption bandwidth of the wave-absorbing material prepared by the invention can be flexibly adjusted within the range of 0.3-1.0 GHz band according to the requirement, and the material has better mechanical and construction properties after being formed and is easy to be adhered to the surfaces of various structural members.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing material preparation, and particularly relates to a low-frequency P-band wave-absorbing material and a preparation method thereof.
Background
In the actual application, the appearance finishing can increase the processing difficulty and the cost, and is influenced by the functionality of the target, so that a plurality of targets cannot adopt the appearance finishing technology.
The wave-absorbing material can make up the defects existing in the appearance finishing, is not influenced by complex appearance, and is more flexible in use, so that the wave-absorbing material is more convenient to apply. With the continuous progress of the technology, the high-frequency (1-18 GHz) wave-absorbing material is relatively fully and mature researched, the popularization and application in the technical field of engineering are achieved, and the actual engineering effect is achieved. However, the conventional wave-absorbing material in the low-frequency P band (0.3-1.0 GHz) hardly has any wave-absorbing performance, or needs a large thickness space to play an absorbing role, and the technical progress and development of the low-frequency wave-absorbing material are severely restricted.
In summary, in order to solve the problems that the wave-absorbing material in the prior art is mainly applied to high frequency, and the low-frequency P-band wave-absorbing material has poor performance and few varieties, it is very necessary to provide a low-frequency P-band wave-absorbing material and a preparation method thereof.
Disclosure of Invention
The invention provides a low-frequency P-band wave-absorbing material and a preparation method thereof, aiming at solving the problems that the wave-absorbing material in the prior art is mainly applied to high frequency, and the low-frequency P-band wave-absorbing material has poor performance and few varieties.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a low-frequency P-band wave-absorbing material, including the steps of:
(1) modifying graphene powder by using a first surfactant to prepare a functionalized graphene dispersion liquid;
(2) compounding the functionalized graphene dispersion liquid with spherical magnetic alloy particles by a high-energy ball milling method to obtain a functionalized graphene/flaky magnetic alloy particle composite absorbent;
(3) coating the functionalized graphene/flaky magnetic alloy particle composite absorbent by using a second surfactant to prepare a low-frequency P-band absorbent;
(4) and mixing the low-frequency P-band absorbent with ethylene propylene diene monomer, and then carrying out rubber mixing and calendering processes to obtain the low-frequency P-band wave-absorbing material.
Preferably, the first surfactant consists of a modifier, a dispersant and a wetting agent; and/or the graphene powder is graphene powder with 3-12 layers; and/or the spherical magnetic alloy particles are one or more of spherical iron-cobalt alloy particles, spherical iron-nickel alloy particles, spherical cobalt-nickel alloy particles and spherical iron-silicon-aluminum alloy particles.
Preferably, in step (1), the amounts of the raw material components are as follows: 65-95 parts of graphene powder, 5-12 parts of a modifier, 0.8-3.2 parts of a dispersant and 1.2-2.6 parts of a wetting agent.
Preferably, in the step (1), the graphene powder and the first surfactant are uniformly stirred, so that the first surfactant performs modification treatment on the graphene powder, thereby preparing the functionalized graphene dispersion liquid; the stirring temperature is 35-75 ℃, and the stirring time is 30-55 min.
Preferably, step (2) comprises the sub-steps of:
(a) mixing the functionalized graphene dispersion liquid prepared in the step (1) with spherical magnetic alloy particles, and performing high-energy ball milling to obtain a mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent;
(b) and filtering the mixed solution to obtain solid powder, and then sequentially cleaning and drying the solid powder to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
Preferably, in step (a): in the process of carrying out the high-energy ball milling, a grinding aid and a process control agent are also added; and/or the ball-material ratio of the high-energy ball mill is (3-20): (1-5), wherein the time of the high-energy ball milling is 6-18 h.
Preferably, the grinding aid is one or more of carbon black, calcium carbonate, calcium titanate and diatomite; and/or the process control agent is one or more of n-hexane, ethanol, ethyl acetate, n-butanol and acetone; and/or the mass ratio of the functionalized graphene dispersion liquid to the spherical magnetic alloy particles to the grinding aid to the process control agent is (20-40): (60-90): (1-3): (50-70).
Preferably, in step (3): the second surfactant is one or more of KH-550, KH-560, KH-570 and BYK-181; and/or the mass ratio of the functionalized graphene/flaky magnetic alloy particle composite absorbent to the second surfactant is (90-120): (1-8).
Preferably, in step (4): the mass ratio of the low-frequency P-band absorbent to the ethylene propylene diene monomer is (60-92): (1-10); and/or in the rubber mixing and calendering process, the raw rubber sheet formed by the low-frequency P wave band absorbent and the ethylene propylene diene monomer is subjected to gradient heating treatment; the gradient warming treatment comprises the following steps: and (3) firstly, preserving the heat of the raw rubber sheet at 80-120 ℃ for 0.5-1 h, and then preserving the heat at 140-150 ℃ for 1-2 h.
In a second aspect, the invention provides a low-frequency P-band wave-absorbing material prepared by the preparation method in the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the method, a novel low-frequency absorbent of the functionalized graphene/flaky magnetic alloy particle composite absorbent is prepared through a proper synthesis process and a preparation method, the composite material of the functionalized graphene and the flaky magnetic alloy particle is obtained, the characteristics of the graphene and the flaky magnetic alloy particle are combined, the advantages of electromagnetic wave loss and absorption of the two materials in a low-frequency state are fully exerted, the requirement on the low-frequency wave-absorbing material is met, and a new thought is provided for expanding the low-frequency P-band wave-absorbing material; the low-frequency P-band wave-absorbing material prepared by the invention has excellent wave-absorbing performance in the frequency band range of 0.3-1.0 GHz.
(2) According to the method, the wave-absorbing material with the functionalized graphene/flaky magnetic alloy particles as the absorbent can keep a good wave-absorbing effect under a thin-layer condition, and the effective absorption bandwidth covers the whole P wave band at 0.3-1.0 GHz; the raw materials for preparing the functionalized graphene dispersion liquid are wide in source and low in cost, and the cost for preparing the wave-absorbing material can be remarkably reduced while the wave-absorbing effect is ensured; meanwhile, abundant raw material sources and simple preparation process are beneficial to the stability of product performance and quality, and the reliability of the low-frequency P-band wave-absorbing material can be improved.
(3) The method has the advantages of low cost, simple preparation process, convenient operation, easy realization of industrial production, reliable performance and stable quality of the prepared product, and not only can play a role in absorbing low-frequency electromagnetic waves, but also has the advantage of easy production and manufacture; the effective absorption bandwidth of the low-frequency P-band wave-absorbing material prepared by the invention can be flexibly adjusted within the range of 0.3-1.0 GHz as required, and the material has good mechanical and construction properties after being formed and is easy to be adhered to the surfaces of various structural members.
Drawings
FIG. 1 is a flow chart of the preparation of the low-frequency P-band wave-absorbing material of the invention.
FIG. 2 is a graph of the reflectivity test result of the low-frequency P-band wave-absorbing material prepared in example 1 of the present invention.
FIG. 3 is a graph of the reflectivity test result of the low-frequency P-band wave-absorbing material prepared in example 2 of the present invention.
In fig. 2 and 3: the abscissa is frequency (in GHz) and the ordinate is reflectivity (in dB).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a low-frequency P-waveband wave-absorbing material, which comprises the following steps:
(1) and (3) modifying (functionalizing) the graphene powder by using a first surfactant to prepare a functionalized graphene dispersion liquid.
(2) Compounding the functionalized graphene dispersion liquid with spherical magnetic alloy particles by a high-energy ball milling method to obtain a functionalized graphene/flaky magnetic alloy particle composite absorbent; in the invention, the high-energy ball mill can provide collision force between the grinding balls and the powder, so that the shape of the magnetic alloy particles is changed from spherical to flaky.
(3) Coating the functionalized graphene/flaky magnetic alloy particle composite absorbent by using a second surfactant to prepare a low-frequency P-band absorbent; in the invention, the time of the coating treatment is, for example, 1-2 h; in the invention, the functionalized graphene/flaky magnetic alloy particle composite absorbent is coated by the second surfactant, on one hand, the magnetic alloy particles belong to metal components and are easy to be oxidized, and a physical protective layer can be formed by coating the surface layer; on the other hand, the functionalized graphene/flaky magnetic alloy particle composite absorbent is coated, so that the dielectric constant of the original magnetic powder can be reduced, the electromagnetic matching capacity is improved, electromagnetic waves can easily penetrate through the surface of the material to enter the interior, and the low-frequency electromagnetic absorption performance is enhanced.
(4) And mixing the low-frequency P-band absorbent with ethylene propylene diene monomer, and then preparing the low-frequency P-band wave-absorbing material (for example, preparing a low-frequency P-band wave-absorbing rubber patch) by rubber mixing and rolling processes.
According to the invention, a first surfactant is used for modifying graphene to prepare a functionalized graphene dispersion liquid, a high-energy ball milling method is used for compounding functionalized graphene and spherical magnetic alloy particles to prepare a functionalized graphene/flaky magnetic alloy particle composite absorbent, a second surfactant is used for coating the functionalized graphene/flaky magnetic alloy particle composite absorbent to obtain a novel low-frequency P waveband absorbent of the functionalized graphene/flaky magnetic alloy particle composite absorbent, and then ethylene propylene diene monomer is selected as a base material to prepare a low-frequency P waveband wave-absorbing rubber patch material, so that a new solution idea is provided for expanding the low-frequency P waveband wave-absorbing material.
The invention creatively prepares the novel low-frequency absorbent of the functionalized graphene/flaky magnetic alloy particle composite absorbent through a proper synthesis process and a preparation method, obtains the composite material of the two, can better combine the characteristics of the graphene and the flaky magnetic alloy particles compared with the material combining the common graphene/spherical magnetic alloy particles, the common graphene/flaky magnetic alloy particles and the functionalized graphene/spherical magnetic alloy particles, fully exerts the advantages of the electromagnetic wave loss and absorption of the two materials in a low-frequency state, provides a new idea for expanding the low-frequency P-waveband wave-absorbing material because the electromagnetic wave is a synthesis wave and consists of electric field and magnetic field energy which are mutually vertical in space, the inventor finds that graphene is a dielectric material, and functionalized graphene can better exert the advantage of electric field loss; the magnetic alloy particles are magnetic materials, the flaky magnetic alloy particles can better exert the advantage of magnetic field loss, and the functionalized graphene and the flaky magnetic alloy particles are reasonably combined, so that electromagnetic waves can be more effectively attenuated in two dimensions of electricity and magnetism, and a good basic condition is created for low-frequency absorption. According to the method, the wave-absorbing material with the functionalized graphene/flaky magnetic alloy particles as the absorbent can keep a good wave-absorbing effect under a thin-layer condition, and the effective absorption bandwidth covers the whole P wave band at 0.3-1.0 GHz; the low-frequency P-band wave-absorbing material prepared by the invention has excellent wave-absorbing performance in the frequency band range of 0.3-1.0 GHz.
According to some preferred embodiments, the first surfactant consists of a modifying agent, a dispersing agent and a wetting agent, in the present invention, the modifying agent may be, for example, one or more of KH-550, KH-560, KH-570; the dispersant may be, for example, an ANTI-tera-204 dispersant; the wetting agent may be, for example, BYK-181 wetting agent; and/or the graphene powder is graphene powder with 3-12 layers; and/or the spherical magnetic alloy particles are one or more of spherical iron-cobalt alloy particles, spherical iron-nickel alloy particles, spherical cobalt-nickel alloy particles and spherical iron-silicon-aluminum alloy particles.
According to some preferred embodiments, in step (1), the raw material components are used in the following amounts:
65-95 parts by weight (for example, 65, 70, 75, 80, 85, 90 or 95 parts by weight) of graphene powder, 5-12 parts by weight (for example, 5, 6, 7, 8, 9, 10, 11 or 12 parts by weight) of a modifier, 0.8-3.2 parts by weight (for example, 0.8, 1.0, 1.5, 1.7, 2.0, 2.5, 3.0 or 3.2 parts by weight) of a dispersant, and 1.2-2.6 parts by weight (for example, 1.2, 1.5, 1.8, 2.0, 2.2, 2.4 or 2.6 parts by weight) of a wetting agent.
According to some preferred embodiments, in the step (1), the graphene powder and the first surfactant are uniformly stirred, so that the first surfactant performs modification treatment on the graphene powder, thereby preparing the functionalized graphene dispersion liquid; the stirring temperature is 35-75 ℃ (for example, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃), and the stirring time is 30-55 min (for example, 30, 35, 40, 45, 50 or 55 min).
According to some preferred embodiments, step (2) comprises the following sub-steps:
(a) mixing the functionalized graphene dispersion liquid prepared in the step (1) with spherical magnetic alloy particles, and performing high-energy ball milling to obtain a mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent;
(b) and filtering the mixed solution to obtain solid powder, and then sequentially cleaning and drying the solid powder to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
According to some preferred embodiments, in step (a): in the process of carrying out the high-energy ball milling, a grinding aid and a process control agent are also added; and/or the ball-material ratio of the high-energy ball mill is (3-20): (1-5), and the time of the high-energy ball milling is 6-18 h (such as 6, 8, 10, 12, 14, 16 or 18 h). In the invention, the ball-to-material ratio of the high-energy ball milling is more preferably (3-6): 1, and the time of the high-energy ball milling is more preferably 10-18 h, so that the spherical magnetic alloy particles can be better ensured to be converted into the flaky magnetic alloy particles, and the prepared low-frequency P-band wave-absorbing material can be better ensured to have more excellent wave-absorbing performance in the frequency band range of 0.3-1.0 GHz. For example, in some preferred embodiments, the high energy ball milling has a ball to material ratio of 16:3, and the high energy ball milling time is 10 hours; in other more preferred embodiments, the high energy ball milling has a ball to material ratio of 4:1 and the high energy ball milling time is 16 hours.
According to some preferred embodiments, the grinding aid is one or more of carbon black, calcium carbonate, calcium titanate, diatomaceous earth; and/or the process control agent is one or more of n-hexane, ethanol, ethyl acetate, n-butanol and acetone; and/or the mass ratio of the functionalized graphene dispersion liquid to the spherical magnetic alloy particles to the grinding aid to the process control agent is (20-40): (60-90): (1-3): (50-70) (e.g., 20:60:1:5:50, 25:65:1.5:60, 25:80:1.5:60, 30:65:1.5:60, 30:80:1.5:60, 30:70:2:65, 40:65:1.5:60, 40:80:1.5:60, or 40:90:3: 70).
According to some preferred embodiments, in step (3): the second surfactant is one or more of KH-550, KH-560, KH-570 and BYK-181; in the invention, silane coupling agents KH-550, KH-560 and KH-570 refer to gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane respectively, wherein BYK-181 refers to a wetting dispersant (wetting agent) with the model number of BYK-181.
According to some preferred embodiments, the mass ratio of the functionalized graphene/flaky magnetic alloy particle composite absorbent to the second surfactant is (90-120): (1-8) (e.g., 90:3, 95:3, 100:5, 110:6, or 120: 8).
According to some preferred embodiments, in step (4): the mass ratio of the low-frequency P-band absorbent to the ethylene propylene diene monomer is (60-92): (1-10) (e.g., 65:9, 70:9, 80:9, or 90: 9); and/or in the rubber mixing and calendering process, the raw rubber sheet formed by the low-frequency P wave band absorbent and the ethylene propylene diene monomer is subjected to gradient heating treatment; the gradient warming treatment comprises the following steps: the raw rubber sheet is first heat-preserved for 0.5-1 h (e.g., 0.5 or 1h) at 80-120 ℃ (e.g., 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃) and then heat-preserved for 1-2 h (e.g., 1, 1.5 or 2h) at 140-150 ℃ (e.g., 140 ℃, 145 ℃ or 150 ℃).
According to some specific embodiments, the preparation process of the low-frequency P-band wave-absorbing material is as follows:
firstly, in step S1, adding graphene powder, a modifier, a dispersant and a wetting agent into a reaction kettle to perform functionalization treatment on graphene, and uniformly stirring to prepare a functionalized graphene dispersion liquid;
next, in step S2, after the spherical magnetic alloy particles, the grinding aid and the process control agent are uniformly mixed, the mixture is added to the functionalized graphene dispersion liquid obtained in step S1, and a high-energy ball milling process is performed in a ball milling tank to obtain a mixed liquid containing the functionalized graphene/sheet-shaped magnetic alloy particle composite absorbent;
in step S3, filtering the mixed solution obtained in step S2, filtering out solid powder, repeatedly cleaning the solid powder for 3-5 times by using absolute ethyl alcohol, transferring the solid powder to a vacuum drying oven, and preserving heat for 2 hours at 40-60 ℃ to prepare the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent;
in step S4, adding the powdery composite absorbent obtained in step S3 into absolute ethyl alcohol, adding a second surfactant while dispersing under high shear, coating the powder, filtering out solid powder after 1.5 hours, repeatedly cleaning the solid powder for 3-5 times by using the absolute ethyl alcohol, transferring the powder to a vacuum drying oven, and preserving heat at 40-60 ℃ for 2 hours to obtain low-frequency P-band absorbent powder;
finally, in step S5, selecting ethylene propylene diene monomer as a base material, mixing a low-frequency P-band absorbent with the ethylene propylene diene monomer, and then preparing the low-frequency P-band wave-absorbing rubber patch through rubber mixing and calendering processes; in the rubber mixing and calendering process, the raw rubber sheet formed by the low-frequency P-band absorbent and the ethylene propylene diene monomer is placed between moulds to be subjected to gradient heating treatment, and the process comprises the following steps: and (4) keeping the temperature at 80-120 ℃ (0.5-1.0 h) → 140-150 ℃ (1-2 h), and finally obtaining the low-frequency P-band wave-absorbing rubber patch.
In a second aspect, the invention provides a low-frequency P-band wave-absorbing material prepared by the preparation method in the first aspect. The product prepared by the invention has reliable performance and stable quality, not only can play a role of absorbing low-frequency electromagnetic waves, but also has the advantage of easy production and manufacture; the effective absorption bandwidth of the low-frequency P-band wave-absorbing material prepared by the invention can be flexibly adjusted within the range of 0.3-1.0 GHz as required, and the material has good mechanical and construction properties after being formed and is easy to be adhered to the surfaces of various structural members.
The present invention will be further described with reference to the following examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples.
Example 1
The low-frequency P-band wave-absorbing material is prepared by the following steps:
functionalized graphene dispersion liquid: weighing 85 parts by weight of graphene powder, 7 parts by weight of KH-550 modifier, 1.7 parts by weight of ANTI-TERRA-204 dispersant and 1.3 parts by weight of BYK-181 wetting agent, placing the materials in an absolute ethyl alcohol solvent, and carrying out high-speed stirring and dispersing treatment by a homogenizer to obtain a uniformly mixed functionalized graphene dispersion liquid.
② the functionalized graphene/sheet magnetic alloy particle composite absorbent: weighing 25 parts of functionalized graphene dispersion liquid; adding 65 parts by weight of spherical iron-cobalt alloy particles, 1.5 parts by weight of calcium carbonate grinding aid and 60 parts by weight of n-butyl alcohol process control agent into functionalized graphene dispersion liquid, wherein the ball-material ratio is 16:3, and performing high-energy ball milling for 10 hours to obtain mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent; and then filtering the mixed solution, filtering out solid powder, repeatedly washing the solid powder for 5 times by using absolute ethyl alcohol, transferring the solid powder to a vacuum drying oven, and preserving heat for 2 hours at 45 ℃ to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
Coating treatment of the functionalized graphene/flaky magnetic alloy particle composite absorbent: weighing 95 parts by weight of the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent obtained in the second step, adding the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent into absolute ethyl alcohol, adding 3 parts by weight of a second surfactant (KH-550) while dispersing under high shear, coating the powder, filtering out solid powder after 1.5 hours, repeatedly cleaning the filtered solid powder with absolute ethyl alcohol for 5 times, transferring the washed solid powder to a vacuum drying oven, and preserving heat at 45 ℃ for 2 hours to obtain the coated low-frequency P-band absorbent.
Fourthly, low-frequency P wave band wave-absorbing rubber paster: weighing 70 parts by weight of coated low-frequency P-band absorbent powder and 9 parts by weight of ethylene propylene diene monomer as matrix materials, and performing gradient heating treatment by placing a raw rubber sheet between molds through rubber mixing and calendering processes: and (5) keeping the temperature for 0.5h → 145 ℃ and keeping the temperature for 1.5h, and finally preparing the low-frequency P-band wave-absorbing rubber patch.
The graph of the reflectivity curve test result of the low-frequency P-band wave-absorbing rubber patch prepared by the embodiment is shown in fig. 2, the reflectivity of the low-frequency P-band wave-absorbing rubber patch in the frequency band range of 0.3-1.0 GHz is not more than-3 dB, the reflectivity of the low-frequency P-band wave-absorbing rubber patch in the frequency band range of 1.0GHz is-6.5 dB, and the low-frequency P-band wave-absorbing rubber patch has very good wave-absorbing performance in the frequency band range of 0.3-1.0 GHz.
Example 2
The low-frequency P-band wave-absorbing material is prepared by the following steps:
functionalized graphene dispersion liquid: weighing 90 parts by weight of graphene powder, 6 parts by weight of KH-550 modifier, 1.5 parts by weight of ANTI-TERRA-204 dispersant and 1.5 parts by weight of BYK-181 wetting agent, placing the materials in an absolute ethyl alcohol solvent, and carrying out high-speed stirring and dispersing treatment by a homogenizer to obtain a uniformly mixed functionalized graphene dispersion liquid.
② the functionalized graphene/sheet magnetic alloy particle composite absorbent: weighing 25 parts of functionalized graphene dispersion liquid; adding 80 parts by weight of spherical iron-nickel alloy particles, 1.5 parts by weight of calcium carbonate grinding aid and 60 parts by weight of n-butyl alcohol process control agent into functionalized graphene dispersion liquid, wherein the ball-material ratio is 16:3, and performing high-energy ball milling for 10 hours to obtain mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent; and then filtering the mixed solution, filtering out solid powder, repeatedly washing the solid powder for 5 times by using absolute ethyl alcohol, transferring the solid powder to a vacuum drying oven, and preserving heat for 2 hours at 45 ℃ to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
Coating treatment of the functionalized graphene/flaky magnetic alloy particle composite absorbent: weighing 90 parts by weight of the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent obtained in the second step, adding the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent into absolute ethyl alcohol, adding 3 parts by weight of a second surfactant (KH-550) while dispersing under high shear, coating the powder, filtering out solid powder after 1.5 hours, repeatedly cleaning the filtered solid powder with absolute ethyl alcohol for 5 times, transferring the washed solid powder to a vacuum drying oven, and preserving heat at 45 ℃ for 2 hours to obtain the coated low-frequency P-band absorbent.
Fourthly, low-frequency P wave band wave-absorbing rubber paster: weighing 65 parts by weight of coated low-frequency P-band absorbent powder and 9 parts by weight of ethylene propylene diene monomer as matrix materials, and placing the sheet rubber between molds for gradient heating treatment through rubber mixing and calendering processes: and (5) keeping the temperature for 0.5h → 145 ℃ and keeping the temperature for 1.5h, and finally preparing the low-frequency P-band wave-absorbing rubber patch.
The reflectivity curve test result chart of the low-frequency P-band wave-absorbing rubber patch prepared by the embodiment is shown in fig. 3, the reflectivity of the low-frequency P-band wave-absorbing rubber patch in the frequency band range of 0.3-1.0 GHz is not more than-3.8 dB, the reflectivity of the low-frequency P-band wave-absorbing rubber patch in the frequency band range of 1.0GHz is-7.2 dB, and the low-frequency P-band wave-absorbing rubber patch has very good wave-absorbing performance in the frequency band range of 0.3-1.0 GHz.
Example 3
Example 3 is essentially the same as example 2, except that:
in the second step, the ball-material ratio is 4:1, and the high-energy ball milling time is 16 h.
The reflectivity of the low-frequency P-band wave-absorbing rubber patch prepared by the embodiment in the frequency band range of 0.3-1.0 GHz is not more than-4.5 dB.
Comparative example 1
The wave-absorbing rubber patch material is prepared by the following steps:
graphene/spherical magnetic alloy particle composite absorbent: and uniformly stirring and mixing 25 parts by weight of graphene powder and 65 parts by weight of spherical iron-cobalt alloy particles to obtain the graphene/spherical magnetic alloy particle composite absorbent.
Preparing the wave-absorbing rubber patch material: weighing 70 parts by weight of the composite absorbent powder obtained in the step I and 9 parts by weight of ethylene propylene diene monomer as matrix materials, and placing the raw rubber sheet between moulds to perform gradient heating treatment by rubber mixing and calendering processes: and (5) keeping the temperature for 0.5h → 145 ℃ for 1.5h, and finally preparing the wave-absorbing rubber patch material.
The reflectivity of the wave-absorbing rubber patch material prepared by the comparative example is not less than-1.5 dB within the frequency band range of 0.3-1.0 GHz.
Comparative example 2
The wave-absorbing rubber patch material is prepared by the following steps:
graphene/sheet-like magnetic alloy particle composite absorbent: uniformly mixing 25 parts by weight of graphene powder, 65 parts by weight of spherical iron-cobalt alloy particles, 1.5 parts by weight of calcium carbonate grinding aid and 60 parts by weight of n-butyl alcohol process control agent according to a ball-material ratio of 16:3, and performing high-energy ball milling for 10 hours to obtain a mixed solution containing the graphene/flaky magnetic alloy particle composite absorbent; and then filtering the mixed solution, filtering out solid powder, repeatedly washing the solid powder for 5 times by using absolute ethyl alcohol, transferring the solid powder to a vacuum drying oven, and preserving heat for 2 hours at 45 ℃ to obtain the powdery graphene/flaky magnetic alloy particle composite absorbent.
Coating treatment of the graphene/flaky magnetic alloy particle composite absorbent: weighing 95 parts by weight of the powdered graphene/flaky magnetic alloy particle composite absorbent obtained in the second step, adding the powdered graphene/flaky magnetic alloy particle composite absorbent into absolute ethyl alcohol, adding 3 parts by weight of a second surfactant (KH-550) while performing high-shear dispersion, performing coating treatment on the powder, filtering out solid powder after 1.5 hours, repeatedly cleaning the filtered solid powder with absolute ethyl alcohol for 5 times, transferring the cleaned solid powder to a vacuum drying oven, and preserving heat at 45 ℃ for 2 hours to obtain the coated composite absorbent.
Preparing the wave-absorbing rubber patch material: weighing 70 parts by weight of the coated composite absorbent powder and 9 parts by weight of ethylene propylene diene monomer as matrix materials, and placing the raw rubber sheet between moulds to perform gradient heating treatment by rubber mixing and calendering processes: and (5) keeping the temperature for 0.5h → 145 ℃ for 1.5h, and finally preparing the wave-absorbing rubber patch material.
The reflectivity of the wave-absorbing rubber patch material prepared by the comparative example is not less than-2.5 dB within the frequency band range of 0.3-1.0 GHz.
Comparative example 3
The wave-absorbing rubber patch material is prepared by the following steps:
functionalized graphene dispersion liquid: weighing 85 parts by weight of graphene powder, 7 parts by weight of KH-550 modifier, 1.7 parts by weight of ANTI-TERRA-204 dispersant and 1.6 parts by weight of BYK-181 wetting agent, placing the materials in an absolute ethyl alcohol solvent, and carrying out high-speed stirring and dispersing treatment by a homogenizer to obtain a uniformly mixed functionalized graphene dispersion liquid.
② the functionalized graphene/spherical magnetic alloy particle composite absorbent: uniformly stirring and mixing 25 parts by weight of functionalized graphene dispersion liquid and 65 parts by weight of spherical iron-cobalt alloy particles to obtain the functionalized graphene/spherical magnetic alloy particle composite absorbent.
Coating treatment of the functionalized graphene/spherical magnetic alloy particle composite absorbent: weighing 95 parts by weight of the powdered functionalized graphene/spherical magnetic alloy particle composite absorbent obtained in the second step, adding into absolute ethyl alcohol, adding KH-5503 parts by weight while dispersing at high shear, coating the powder, filtering out solid powder after 1.5h, repeatedly cleaning the solid powder with absolute ethyl alcohol for 5 times, transferring to a vacuum drying oven, and preserving heat at 45 ℃ for 2h to obtain the coated absorbent.
Preparing the wave-absorbing rubber patch material: weighing 70 parts by weight of the coated absorbent powder and 9 parts by weight of ethylene propylene diene monomer as matrix materials, and performing gradient heating treatment on the raw rubber sheet placed between dies through rubber mixing and calendering processes: and (5) keeping the temperature for 0.5h → 145 ℃ for 1.5h, and finally preparing the wave-absorbing rubber patch material.
The reflectivity of the wave-absorbing rubber patch material prepared by the comparative example is not less than-2 dB in the frequency band range of 0.3-1.0 GHz.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: not including the third step, namely not coating the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent obtained in the second step, but directly weighing 65 parts by weight of the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent obtained in the second step and 9 parts by weight of ethylene propylene diene monomer as base materials, and performing gradient heating treatment by placing the raw rubber sheet between dies through rubber mixing and calendering processes: and (5) keeping the temperature for 0.5h → 145 ℃ for 1.5h, and finally preparing the wave-absorbing rubber patch material.
The reflectivity of the wave-absorbing rubber patch material prepared by the comparative example is not less than-3 dB in the frequency band range of 0.3-1.0 GHz.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that:
functionalized graphene dispersion liquid: weighing 50 parts by weight of graphene powder, 6 parts by weight of KH-560 modifier, 1.5 parts by weight of ANTI-TERRA-204 dispersant and 0.15 part by weight of BYK-181 wetting agent, placing the materials in an absolute ethyl alcohol solvent, and carrying out high-speed stirring and dispersing treatment by a homogenizer to obtain a uniformly mixed functionalized graphene dispersion solution.
② the functionalized graphene/sheet magnetic alloy particle composite absorbent: weighing 15 parts by weight of functionalized graphene dispersion liquid; adding 80 parts by weight of spherical iron-nickel alloy particles, 1.5 parts by weight of calcium carbonate grinding aid and 60 parts by weight of n-butyl alcohol process control agent into functionalized graphene dispersion liquid, wherein the ball-material ratio is 16:3, and performing high-energy ball milling for 10 hours to obtain mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent; and then filtering the mixed solution, filtering out solid powder, repeatedly washing the solid powder for 5 times by using absolute ethyl alcohol, transferring the solid powder to a vacuum drying oven, and preserving heat for 2 hours at 45 ℃ to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
The reflectivity of the wave-absorbing rubber patch material prepared by the comparative example is not less than-3 dB in the frequency band range of 0.3-1.0 GHz.
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that:
functionalized graphene dispersion liquid: weighing 50 parts by weight of graphene powder, 6 parts by weight of KH-560 modifier, 1.5 parts by weight of ANTI-TERRA-204 dispersant and 1.6 parts by weight of BYK-181 wetting agent, placing the materials in an absolute ethyl alcohol solvent, and carrying out high-speed stirring and dispersing treatment by a homogenizer to obtain a uniformly mixed functionalized graphene dispersion solution.
② the functionalized graphene/sheet magnetic alloy particle composite absorbent: weighing 50 parts by weight of functionalized graphene dispersion liquid; adding 60 parts by weight of spherical iron-silicon-aluminum alloy particles, 1.5 parts by weight of calcium carbonate grinding aid and 60 parts by weight of n-butyl alcohol process control agent into the functionalized graphene dispersion liquid, wherein the ball-material ratio is 16:3, and performing high-energy ball milling for 10 hours to obtain mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent; and then filtering the mixed solution, filtering out solid powder, repeatedly washing the solid powder for 5 times by using absolute ethyl alcohol, transferring the solid powder to a vacuum drying oven, and preserving heat for 2 hours at 45 ℃ to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
The reflectivity of the wave-absorbing rubber patch material prepared by the comparative example is not less than-3 dB in the frequency band range of 0.3-1.0 GHz.
The low-frequency P-band wave-absorbing material prepared by the invention has the advantages of low cost, simple preparation process, convenient operation, easy realization of industrial production, reliable performance and stable quality of the prepared product, can play a role in absorbing low-frequency electromagnetic waves, and is easy to produce and manufacture.
Finally, the description is as follows: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the embodiments can still be modified, or some technical features can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the present invention in its spirit and scope.
Claims (6)
1. A preparation method of a low-frequency P-waveband wave-absorbing material is characterized by comprising the following steps:
(1) modifying graphene powder by using a first surfactant to prepare a functionalized graphene dispersion liquid; the first surfactant is composed of a modifier, a dispersant and a wetting agent; the modifier is one or more of KH-550, KH-560 and KH-570; the dispersant is an ANTI-TERRA-204 dispersant; the wetting agent is a BYK-181 wetting agent; in the step (1), the following raw material components are used: 65-95 parts of graphene powder, 5-12 parts of a modifier, 0.8-3.2 parts of a dispersant and 1.2-2.6 parts of a wetting agent;
(2) compounding the functionalized graphene dispersion liquid with spherical magnetic alloy particles by a high-energy ball milling method to obtain a functionalized graphene/flaky magnetic alloy particle composite absorbent;
(3) coating the functionalized graphene/flaky magnetic alloy particle composite absorbent by using a second surfactant to prepare a low-frequency P-band absorbent; in step (3): the second surfactant is one or more of KH-550, KH-560, KH-570 and BYK-181; the mass ratio of the functionalized graphene/flaky magnetic alloy particle composite absorbent to the second surfactant is (90-120): (1-8);
(4) mixing the low-frequency P-band absorbent with ethylene propylene diene monomer, and then preparing the low-frequency P-band wave-absorbing material through rubber mixing and calendering processes;
the step (2) comprises the following substeps:
(a) mixing the functionalized graphene dispersion liquid prepared in the step (1) with spherical magnetic alloy particles, and performing high-energy ball milling to obtain a mixed liquid containing the functionalized graphene/flaky magnetic alloy particle composite absorbent; in the step (a), a grinding aid and a process control agent are also added in the process of carrying out the high-energy ball milling; the grinding aid is one or more of carbon black, calcium carbonate, calcium titanate and diatomite; the process control agent is one or more of n-hexane, ethanol, ethyl acetate, n-butanol and acetone; the mass ratio of the functionalized graphene dispersion liquid to the spherical magnetic alloy particles to the grinding aid to the process control agent is (20-40): (60-90): (1-3): (50-70);
(b) and filtering the mixed solution to obtain solid powder, and then sequentially cleaning and drying the solid powder to obtain the powdered functionalized graphene/flaky magnetic alloy particle composite absorbent.
2. The method of claim 1, wherein:
the graphene powder comprises 3-12 layers of graphene powder; and/or
The spherical magnetic alloy particles are one or a compound of more of spherical iron-cobalt alloy particles, spherical iron-nickel alloy particles, spherical cobalt-nickel alloy particles and spherical iron-silicon-aluminum alloy particles.
3. The production method according to claim 1 or 2, characterized in that:
in the step (1), uniformly stirring the graphene powder and the first surfactant to enable the first surfactant to modify the graphene powder, thereby preparing the functionalized graphene dispersion liquid;
the stirring temperature is 35-75 ℃, and the stirring time is 30-55 min.
4. The method of claim 1, wherein in step (a):
the ball-material ratio of the high-energy ball mill is (3-20): (1-5), wherein the time of the high-energy ball milling is 6-18 h.
5. The production method according to claim 1, wherein in step (4):
the mass ratio of the low-frequency P-band absorbent to the ethylene propylene diene monomer is (60-92): (1-10); and/or
In the rubber mixing and calendering process, the raw rubber sheet formed by the low-frequency P wave band absorbent and the ethylene propylene diene monomer is subjected to gradient heating treatment;
the gradient warming treatment comprises the following steps: and (3) firstly, preserving the heat of the raw rubber sheet at 80-120 ℃ for 0.5-1 h, and then preserving the heat at 140-150 ℃ for 1-2 h.
6. The low-frequency P wave-band wave-absorbing material prepared by the preparation method of any one of claims 1 to 5.
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| CN113278400B (en) * | 2021-07-13 | 2021-09-24 | 信维通信（江苏）有限公司 | Graphene foam composite wave-absorbing material and preparation method thereof |
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