CN111320165B - Graphene oxide/carbonyl iron composite material, preparation method thereof and graphene-based wave-absorbing material - Google Patents
Graphene oxide/carbonyl iron composite material, preparation method thereof and graphene-based wave-absorbing material Download PDFInfo
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Abstract
The invention provides a graphene oxide/carbonyl iron composite material, which comprises carbonyl iron and a graphene oxide layer compounded on the surface of the carbonyl iron; the graphene oxide/carbonyl iron composite material has a core-shell structure. According to the invention, a combination mode of graphene oxide and carbonyl iron is adopted, a large amount of oxygen-containing groups exist on the surface of the graphene oxide, so that the graphene oxide is more favorable for chemical combination with the carbonyl iron, a specific compounding process is adopted, the graphene oxide is coated on the surface of the carbonyl iron, a wave absorber structure with a special core-shell structure is formed, the dispersion performance of the graphene oxide and the carbonyl iron is improved, the graphene oxide is not agglomerated, the product is compounded uniformly, and the advantages of the two materials are combined more effectively, so that the graphene oxide/carbonyl iron composite wave absorber material has excellent electromagnetic absorption performance, has good application prospect in the electromagnetic wave absorption field, and is more favorable for application and popularization of industrial mass production.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, relates to a graphene oxide/carbonyl iron composite material and a preparation method thereof, and a wave-absorbing material, and particularly relates to a graphene oxide/carbonyl iron composite wave-absorbing material and a preparation method thereof, and a graphene-based wave-absorbing material.
Background
The rapid development of the current science and technology makes the electronic products widely popularized and greatly facilitates the life of people. Along with the rapid development of microwave and communication technologies, serious threat of electromagnetic pollution to environment and biological safety is increasingly emphasized and cannot be ignored, and the electromagnetic wave is the fourth pollution after air pollution, water pollution and noise pollution, and in modern families, electromagnetic waves directly or indirectly harm human health along with the action of 'electronic smoke'. The protection and shielding of electromagnetic radiation have received general public attention, and thus, research and development of efficient wave-absorbing materials have become a hotspot for research in the industry. In addition, the research of the high-efficiency wave-absorbing material has important significance for stealth of weapon equipment and improvement of the survivability of a weapon system. Therefore, the preparation of a novel wave-absorbing material and excellent electromagnetic wave absorption ability in as wide an electromagnetic wave range as possible have become an important issue that human beings cannot neglect.
Graphene is a monolayer of carbon atoms closely packed into a two-dimensional hexagonal honeycomb lattice structure, with the carbon atoms being connected by sp2 hybridization. Microscopically, the monolayer graphene film is not a two-dimensional flat structure, but a micro-wavy monolayer structure stable on a nano scale, and is the only two-dimensional free-state atomic crystal found at present; macroscopically, graphene can warp into zero-dimensional fullerenes, rolled into one-dimensional carbon nanotubes, or stacked into three-dimensional graphite. The existence of stable carbon six-membered rings in the unique two-dimensional periodic honeycomb lattice structure of graphene endows the graphene with excellent performance: the thickness of the single-layer graphene is only 0.35nm, and the single-layer graphene is the lightest and thinnest material known at present; electron mobility at room temperature of 2×10 5 cm 2 ·V -1 ·s -1 Is 1/300 of the light speed, and the theoretical specific surface area can reach 2630m 2 ·g -1 The light absorption of the whole wave band is only 2.3 percent, and the heat conductivity is as high as 5000 W.m -1 ·K -1 The Young's modulus exceeds 1100GPa, the tensile strength exceeds 130GPa, the toughness is very good, and when external mechanical force is applied, carbon atoms can adapt to the external force through bending deformation without rearranging the carbon atoms, so that the stability of the structure is maintained. These features make it well suited for use in a variety of disciplines and fields.
Particularly, graphene has a very high dielectric constant, can be polarized by an external magnetic field in an electromagnetic field, and an internal electric dipole of the graphene relaxes along with the movement of the electric field, so that part of electric energy is consumed to heat the dielectric medium, namely, the dielectric medium is easily polarized in the external electromagnetic field to generate dielectric loss. Therefore, the method has wide application prospect in the field of wave-absorbing materials. However, a single graphene sheet layer is easy to penetrate by electromagnetic waves and loses electromagnetic wave absorption capacity, and meanwhile, a single high dielectric loss also causes difficulty in impedance matching. Therefore, by compounding graphene with other electromagnetic absorption materials, electromagnetic waves can be prevented from directly transmitting by the barrier effect between quantum dot matrixes and the steric hindrance effect after penetrating into the composite materials, and the effect of reducing the frequency of the electromagnetic waves is achieved. However, the defect that graphene is easy to agglomerate also influences the application of the graphene in the field of wave-absorbing materials.
Therefore, how to find a proper graphene composite material has excellent wave absorbing performance, can ensure that the graphene material is uniformly dispersed and is not agglomerated, and becomes an important problem to be solved urgently by various industry manufacturers and first-line research personnel.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a graphene oxide/carbonyl iron composite material, a preparation method thereof and a wave-absorbing material, in particular to a graphene oxide/carbonyl iron composite wave-absorbing material.
The invention provides a graphene oxide/carbonyl iron composite material, which comprises carbonyl iron and a graphene oxide layer compounded on the surface of the carbonyl iron;
the graphene oxide/carbonyl iron composite material has a core-shell structure.
Preferably, the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100;
the thickness of the graphene oxide layer is 0.3-10 nm;
the particle size of the carbonyl iron particles is 0.1-5 mu m.
Preferably, the particle size of the graphene oxide/carbonyl iron composite material particles is 0.1-5 mu m;
carbonyl iron particles are further compounded on the surface of the graphene oxide layer;
and the particle size of carbonyl iron particles compounded on the surface of the graphene oxide layer is 5-100 nm.
The invention also provides a preparation method of the graphene oxide/carbonyl iron composite material, which comprises the following steps:
a) Premixing carbonyl iron and graphene oxide aqueous solution to obtain a precursor solution;
b) Grinding and homogenizing emulsification are carried out on the precursor solution obtained in the steps, and mixture powder is obtained after post treatment;
c) And sintering the mixture powder obtained in the steps to obtain the graphene oxide/carbonyl iron composite material.
Preferably, the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100;
the carbonyl iron comprises carbonyl iron aqueous solution;
the mass concentration of the carbonyl molten iron solution is 1% -5%;
the mass concentration of the graphene oxide aqueous solution is 0.05 per mill-1%.
Preferably, the carbonyl molten iron solution is obtained by pre-ball milling carbonyl iron powder and water;
the time of the pre-ball milling is 0.5-5 h;
the particle size after the pre-ball milling is 2-20 mu m;
the premixing comprises stirring and mixing;
the premixing time is 0.5-2 h.
Preferably, the milling includes ball milling and sand milling;
the grinding time is 1-15 h;
the homogenizing emulsification comprises high-speed shearing homogenizing emulsification;
the homogenizing and emulsifying time is 10-50 min;
the rotational speed of the homogenizing emulsification is 5000-15000 r/min.
Preferably, the ball milling time is 0.5-5 hours;
the rotation speed of the ball milling is 400-800 r/min;
the sanding time is 0.5-10 h;
the rotational speed of the sand grinding is 1500-3000 r/min;
the particle size of the sand grinding medium is 1.2-1.4 mm.
Preferably, the specific steps of the post-treatment are as follows:
filtering the homogenized and emulsified mixed solution to obtain mixed wet powder, and drying to obtain mixed powder;
the filtering comprises bundling filtering;
the water content of the mixed wet powder is 10% -25%;
the drying time is 4-20 h;
the temperature of the drying is 80-150 ℃;
the sintering temperature is 250-350 ℃;
the sintering time is 4-12 h.
The invention also provides a wave-absorbing material, which comprises the graphene oxide/carbonyl iron composite material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
The invention provides a graphene oxide/carbonyl iron composite material, which comprises carbonyl iron and a graphene oxide layer compounded on the surface of the carbonyl iron; the graphene oxide/carbonyl iron composite material has a core-shell structure. Compared with the prior art, the graphene-based material is used as a wave-absorbing product independently, is easy to penetrate by electromagnetic waves, and can cause difficulty in impedance matching. The invention provides a graphene oxide/carbonyl iron composite material, carbonyl iron is a typical magnetic loss material, belongs to a second-generation electromagnetic absorption material, has better electromagnetic absorption performance,
aiming at the existing graphene/carbonyl iron composite material, such as CN106479433, concentrated hydrochloric acid is used in the reaction, so that the method has a certain operation risk, and the two materials cannot be effectively compounded by ultrasonic mechanical stirring; the problem of dispersion of graphene in the composite material cannot be effectively solved, and the technical scheme for realizing industrialization is not realized. For other graphene/carbonyl iron composite materials, although carbonyl iron powder plays a role in effectively supporting dispersed graphene sheets, the problem of re-agglomeration caused by weak binding force still exists. According to the invention, graphene oxide is particularly selected as a research direction, a large number of oxygen-containing groups (such as hydroxyl, carboxyl, epoxy groups and the like) exist on the surface of the graphene oxide, and the oxygen-containing groups on the surface of the graphene oxide are used as targets for combining with nano materials, so that the graphene oxide and carbonyl iron are chemically combined, and electromagnetic waves can be prevented from directly transmitting by barrier effect among quantum dot matrixes and steric hindrance effect after penetrating into the composite material, thereby achieving the effect of reducing the frequency of the electromagnetic waves.
According to the invention, the problem that graphene oxide film is thin and easy to agglomerate is solved, the graphene oxide film is difficult to disperse and compound with carbonyl iron effectively, a specific compounding process is adopted, graphene oxide is coated on the surface of carbonyl iron to form a special composite material with a core-shell structure, the dispersion performance of graphene oxide and carbonyl iron is improved, graphene oxide is not agglomerated, the product is compounded uniformly, the problem of agglomeration of the composite material is effectively solved, the advantages of the two materials are combined more effectively, so that the graphene oxide/carbonyl iron composite wave-absorbing material has excellent electromagnetic absorption performance, has good application prospect in the electromagnetic wave absorption field, and is better used in the fields of military industry, consumer electronics and the like. Meanwhile, the preparation method of the composite material provided by the invention has the advantages of simple process, mild conditions, safety and environmental protection, and is more beneficial to the application and popularization of industrial mass production.
Experimental results show that the graphene oxide/carbonyl iron composite wave-absorbing material prepared by the method has excellent electromagnetic absorption performance and heat conduction performance.
Drawings
FIG. 1 is a schematic process flow diagram of a preparation process provided in an embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a graphene oxide/carbonyl iron composite material prepared according to example 1 of the present invention;
FIG. 3 is a transmission electron micrograph of a graphene oxide/carbonyl iron composite material prepared according to example 1 of the present invention;
fig. 4 is a graph showing the wave absorbing performance of the wave absorber prepared from the graphene oxide/carbonyl iron composite material according to the embodiment of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs conventional purity used in the field of analytical purity or wave-absorbing materials.
The invention provides a graphene oxide/carbonyl iron composite material, which comprises carbonyl iron and a graphene oxide layer compounded on the surface of the carbonyl iron;
the graphene oxide/carbonyl iron composite material has a core-shell structure.
In the graphene oxide/carbonyl iron composite material, the parameter selection and the source of the graphene oxide are not particularly limited, the graphene oxide is prepared according to a conventional method or purchased commercially according to conventional parameters and sources well known to those skilled in the art, and the thickness of the graphene oxide sheet layer is preferably 0.3-10 nm, more preferably 0.5-8 nm, more preferably 1-5 nm, and more preferably 2-4 nm according to practical application conditions, product requirements and quality requirements.
The present invention is not particularly limited in principle, and the composite is defined by a composite well known to those skilled in the art, and the special structure of the graphene oxide/carbonyl iron composite material is preferably one or more of cladding, loading, attaching, stacking, depositing and doping, more preferably cladding, loading, attaching, stacking, depositing or doping, and even more preferably cladding, that is, the graphene oxide/carbonyl iron composite material of the present invention has a core-shell structure, wherein the graphene oxide layer is a shell, and the carbonyl iron particles are cores.
The invention basically has no special limitation on the proportion of each component in the graphene oxide/carbonyl iron composite material, and the skilled person can select and adjust the components according to practical application conditions, product requirements and quality requirements, so that the invention better improves the dispersion performance of graphene oxide and carbonyl iron, reduces agglomeration, is uniform in compounding, improves the electromagnetic absorption performance of the composite wave-absorbing material, and the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100, more preferably (1 to 15): 100, more preferably (3 to 12): 100, more preferably (5 to 10): 100.
the graphene oxide/carbonyl iron composite material has a core-shell structure, a graphene oxide layer is a shell, carbonyl iron particles are a core, and the graphene oxide layer is coated on the surface of carbonyl iron. The carbonyl iron particles are spherical carbonyl iron.
The specific parameters of the graphene oxide/carbonyl iron composite material are not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, so that the dispersion performance of graphene oxide and carbonyl iron is better improved, agglomeration is reduced, the composite is uniform, and the electromagnetic absorption performance of the composite wave-absorbing material is improved, and the particle size of carbonyl iron particles is preferably 0.1-5 mu m, more preferably 0.5-4 mu m, and even more preferably 1-3 mu m. The particle diameter (microscopic particle diameter) of the graphene oxide/carbonyl iron composite particles is preferably 0.1 to 5 μm, more preferably 0.6 to 4.1 μm, and still more preferably 1.1 to 3.1 μm.
In the graphene oxide/carbonyl iron composite material provided by the invention in the above steps, carbonyl iron particles, more preferably small carbonyl iron particles (nanoparticles), are attached to the surface of the graphene oxide, and the carbonyl iron particles can be spherical, granular or irregularly shaped; the graphene oxide/carbonyl iron core-shell structure can be independently loaded on graphene oxide sheets or on the surface of the graphene oxide/carbonyl iron core-shell structure. According to the invention, the carbonyl iron particles compounded on the surface of the graphene oxide layer can be better supported between graphene oxide sheets, so that the carbonyl iron particles are more uniformly dispersed, and the graphene oxide is not agglomerated.
The specific parameters of the carbonyl iron small particles are not particularly limited, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the particle size of the carbonyl iron small particles is preferably 5-100 nm, more preferably 15-90 nm, more preferably 35-70 nm, and more preferably 45-60 nm.
The graphene oxide/carbonyl iron composite material provided by the invention has the advantages that the traditional graphene oxide/carbonyl iron composite mode is abandoned, the graphene oxide material is adopted, the combined target point is increased, the binding force between the composite materials is improved, the mode that the traditional particles are attached to graphene sheets is changed, the core-shell mode of a specific coating structure is adopted, and the carbonyl iron particles on the sheets are combined, so that the dispersion performance of graphene oxide and carbonyl iron is better improved, the agglomeration of graphene oxide is reduced, the uniform dispersion of carbonyl iron is improved, the electromagnetic absorption performance of the composite wave-absorbing material is further improved, and the composite wave-absorbing material has better stability. The composite material provided by the invention realizes the spatial multi-structure compounding of carbonyl iron in graphene oxide sheets, adopts graphene oxide, conducts heat but does not conduct electricity, has the voltage breakdown prevention effect, and also has electromagnetic absorption and heat conduction characteristics.
The invention also provides a preparation method of the graphene oxide/carbonyl iron composite material, which comprises the following steps:
a) Premixing carbonyl iron and graphene oxide aqueous solution to obtain a precursor solution;
b) Grinding and homogenizing emulsification are carried out on the precursor solution obtained in the steps, and mixture powder is obtained after post treatment;
c) And sintering the mixture powder obtained in the steps to obtain the graphene oxide/carbonyl iron composite material.
The selection and composition of the raw materials and the corresponding preferred principles in the preparation method of the graphene oxide/carbonyl iron composite material can be corresponding to the selection and composition of the raw materials corresponding to the graphene oxide/carbonyl iron composite material and the corresponding preferred principles, and are not described in detail herein.
Firstly, premixing carbonyl iron and graphene oxide aqueous solution to obtain a precursor solution.
The method is in principle not particularly limited to the adding mode and specific parameters of the carbonyl iron, and a person skilled in the art can select and adjust the method according to actual production conditions, product requirements and quality requirements. The mass concentration of the carbonyl molten iron solution is preferably 1% -5%, more preferably 1.5% -4.5%, more preferably 2% -4%, and more preferably 2.5% -3.5%.
The invention is in principle not particularly limited to the specific source of the carbonyl molten iron solution, and a person skilled in the art can select and adjust the carbonyl molten iron solution according to actual production conditions, product requirements and quality requirements. The time of the preliminary ball milling according to the present invention is preferably 0.5 to 5 hours, more preferably 1.5 to 4 hours, and still more preferably 2.5 to 3 hours. The particle diameter after the preliminary ball milling, that is, the particle diameter of carbonyl iron powder in the carbonyl iron aqueous solution, is preferably 2 to 20. Mu.m, more preferably 5 to 17. Mu.m, still more preferably 8 to 15. Mu.m, still more preferably 10 to 12. Mu.m.
The parameters of the graphene oxide are not particularly limited in the principle of the invention, and can be known to those skilled in the artThe preparation method is used for better improving the dispersion performance of graphene oxide and carbonyl iron, reducing agglomeration, uniformly compounding and improving the electromagnetic absorption performance of the composite wave-absorbing material according to the actual application condition, the compounding condition and the product performance, wherein the thickness of the graphene oxide is preferably 0.8-1.6 nm, more preferably 0.9-1.5 nm, more preferably 1.0-1.4 nm, and more preferably 1.1-1.3 nm. The number of the graphene oxide sheets of the present invention is preferably 1 to 5, 2 to 4, or 1 to 3, and more preferably the ratio of the graphene oxide sheets of 5 or less is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The graphene oxide sheet according to the present invention preferably has a sheet diameter of 7 to 20. Mu.m, more preferably 10 to 18. Mu.m, and still more preferably 12 to 15. Mu.m. The specific surface area of the graphene oxide is preferably 400-600 m 2 Preferably 420 to 580m 2 Preferably 450 to 550m 2 /g。
The specific parameters of the graphene oxide aqueous solution are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, so that the dispersion performance of graphene oxide and carbonyl iron is better improved, agglomeration is reduced, the composition is uniform, and the electromagnetic absorption performance of the composite wave-absorbing material is improved, wherein the mass concentration of the graphene oxide aqueous solution is preferably 0.05-1%, more preferably 0.1-5%, more preferably 0.5-1%, and more preferably 0.6-0.9%.
The invention has no special limitation on the adding proportion of the carbonyl iron and the graphene oxide in principle, and the person skilled in the art can select and adjust the adding proportion according to the actual application situation, the product requirement and the quality requirement, and the invention is used for better improving the dispersion property of the graphene oxide and the carbonyl iron, reducing agglomeration, uniformly compounding and improving the electromagnetic absorption property of the composite wave-absorbing material, wherein the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100, more preferably (1 to 15): 100, more preferably (3 to 12): 100, more preferably (5 to 10): 100.
the method and parameters of the premixing are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements. The premixing time is preferably 0.5 to 2 hours, more preferably 0.8 to 1.8 hours, and still more preferably 1.0 to 1.5 hours.
The precursor solution obtained in the steps is ground and homogenized and emulsified, and the mixture powder is obtained after post-treatment.
The invention particularly adopts a mechanical treatment mode of grinding and homogenizing emulsification, so that uniform compounding of carbonyl iron and graphene oxide is achieved, and a special core-shell structure of the carbonyl iron coated by the graphene oxide is realized. The invention better improves the dispersion performance of graphene oxide and carbonyl iron, reduces agglomeration, is uniform in compounding and improves the electromagnetic absorption performance of the composite wave-absorbing material, and the grinding is preferably carried out by adopting ball milling and sand milling respectively, and more preferably is carried out by sequentially carrying out ball milling and sand milling. The time for the grinding according to the present invention is preferably 1 to 15 hours, more preferably 3 to 12 hours, and still more preferably 5 to 10 hours.
The specific parameters of the ball milling and the sand milling are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, so that the dispersion performance of graphene oxide and carbonyl iron is better improved, agglomeration is reduced, the composite is uniform, and the electromagnetic absorption performance of the composite wave-absorbing material is improved, wherein the ball milling time is preferably 0.5-5 h, more preferably 1.5-4 h, and even more preferably 2.5-3 h. The rotation speed of the ball mill is preferably 400-800 r/min, more preferably 450-750 r/min, more preferably 500-700 r/min, and more preferably 550-650 r/min. The time for the sanding is preferably 0.5 to 10 hours, more preferably 2.5 to 8 hours, and still more preferably 4.5 to 6 hours. The rotational speed of the sanding is preferably 1500-3000 r/min, more preferably 1800-2700 r/min, and even more preferably 2000-2500 r/min. The particle size of the sanded sanding medium is preferably 1.2 to 1.4mm, more preferably 1.22 to 1.38mm, and even more preferably 1.25 to 1.35mm.
The invention is not particularly limited in principle to specific parameters of the homogeneous emulsification, and a person skilled in the art can select and adjust the parameters according to actual production conditions, product requirements and quality requirements. The time for homogenizing and emulsifying is preferably 10 to 50 minutes, more preferably 15 to 45 minutes, still more preferably 20 to 40 minutes, and still more preferably 25 to 35 minutes. The rotational speed of the homogenizing emulsification is preferably 5000 to 15000r/min, more preferably 7000 to 13000r/min, and still more preferably 9000 to 11000r/min.
The invention further improves the electromagnetic absorption performance of the composite wave-absorbing material, ensures the dispersion performance and uniform compounding of graphene oxide and carbonyl iron, and is a complete and refined preparation process, and the specific steps of the post-treatment are preferably as follows:
filtering the homogenized and emulsified mixed solution to obtain mixed wet powder, and drying to obtain mixed powder.
The method and parameters of the filtration are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements. The water content of the mixed wet powder after filtration is preferably 10-25%, more preferably 12-23%, and even more preferably 15-20%.
The invention is in principle not particularly limited to the parameters of the drying, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, and the invention is used for better improving the dispersion performance of graphene oxide and carbonyl iron, reducing agglomeration, uniformly compounding and improving the electromagnetic absorption performance of the composite wave-absorbing material, wherein the temperature of the drying is preferably 80-150 ℃, more preferably 90-140 ℃, more preferably 100-130 ℃, and more preferably 110-120 ℃.
Finally, sintering the mixture powder obtained in the steps to obtain the graphene oxide/carbonyl iron composite material.
The sintering parameters are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, so that the dispersion performance of graphene oxide and carbonyl iron is better improved, agglomeration is reduced, the composite is uniform, and the electromagnetic absorption performance of the composite wave-absorbing material is improved, wherein the sintering temperature is preferably 250-350 ℃, more preferably 270-330 ℃, and more preferably 290-310 ℃. The sintering time is preferably 4 to 12 hours, more preferably 5 to 11 hours, still more preferably 6 to 10 hours, and still more preferably 7 to 9 hours.
The invention further ensures the performance of the product, perfects and refines the process flow, and the specific steps of the preparation process can be as follows:
taking carbonyl iron powder, adding a certain amount of ultrapure water, adding a horizontal ball mill, ball milling to obtain carbonyl iron water solution, and mixing and stirring the prepared carbonyl iron water solution and graphene oxide water solution to obtain precursor solution.
2, adding the precursor solution obtained in the step 1 into a horizontal ball mill for ball milling, adding a sand mill for sand milling, and adding a high-speed shearing emulsifying machine for high-speed shearing emulsification to obtain a mixed solution;
3, carrying out solid-liquid separation on the mixed solution obtained in the step 2 through a cluster type multi-tube filter to obtain mixed wet powder with the water content of 10% -25%, and drying the mixed wet powder through a vacuum drying box to obtain mixed dry powder;
and 4, adding the mixed dry powder obtained in the step 3 into a continuous rotary furnace for sintering, and adding the materials into a superfine material pulverizer in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, wherein the particle size is 5-20 mu m, can be 8-18 mu m, and can be 10-15 mu m.
Referring to fig. 1, fig. 1 is a schematic process flow diagram of a preparation process according to an embodiment of the present invention.
The invention also provides a wave-absorbing material, which comprises the graphene oxide/carbonyl iron composite material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
The specific form and the form of the wave-absorbing material are not particularly limited, the wave-absorbing material is a specific form and form of the wave-absorbing material which are well known to those skilled in the art, the person skilled in the art can select and adjust the wave-absorbing material according to actual production conditions, product requirements and quality requirements, and the wave-absorbing material is a graphene-based wave-absorbing material which contains or is only the graphene oxide/carbonyl iron composite material prepared by the method. The graphene oxide/carbonyl iron composite material or the wave-absorbing material provided by the invention has excellent wave-absorbing performance.
The invention provides a graphene oxide/carbonyl iron composite wave-absorbing material and a preparation method thereof, wherein the graphene oxide/carbonyl iron composite wave-absorbing material adopts a combination mode of graphene oxide and carbonyl iron, a large number of oxygen-containing groups (such as hydroxyl groups, carboxyl groups, epoxy groups and the like) exist on the surface of the graphene oxide, the oxygen-containing groups on the surface of the graphene oxide are used as targets combined with nano materials, and the graphene oxide and carbonyl iron are chemically combined, so that electromagnetic waves can be prevented from directly transmitting by quantum dot matrix barrier effect and steric hindrance effect after penetrating into the composite material, and the effect of reducing electromagnetic wave frequency is achieved.
According to the invention, a specific compounding process is adopted to obtain graphene oxide coated on the surface of carbonyl iron to form a special wave absorber structure, namely, the graphene oxide coated on the surface of carbonyl iron to form a composite material with a core-shell structure, and small carbonyl iron particles are loaded on the surface of a graphene oxide sheet layer to better support the graphene oxide sheet layer, meanwhile, the carbonyl iron can be compounded better based on the polyfunctional group of the graphene oxide as a target point, so that the dispersion performance of the graphene oxide and the carbonyl iron is better improved, the graphene oxide is not agglomerated, the product is compounded uniformly, the agglomeration problem of the composite material is effectively solved, the advantages of the two materials are combined more effectively, so that the graphene oxide/carbonyl iron composite wave absorber material has excellent electromagnetic absorption performance, has good application prospect in the electromagnetic wave absorption field, and is better used in the fields of military industry, consumer electronics and the like.
Meanwhile, the traditional ultrasonic mode is abandoned, and the graphene oxide wave absorber is obtained by only mixing the graphene oxide solution and the carbonyl iron solution, performing high-speed shearing emulsification, ball milling and sand milling, performing solid-liquid separation, and then performing vacuum drying, sintering and crushing. The preparation method has the advantages of simple process, mild conditions, safety and environmental protection, is more beneficial to the application and popularization of industrial mass production, and is a technical scheme suitable for industrial continuous production.
Experimental results show that the graphene oxide/carbonyl iron composite wave-absorbing material prepared by the method has excellent electromagnetic absorption performance and heat conduction performance.
In order to further illustrate the present invention, the graphene oxide/carbonyl iron composite material, the preparation method thereof and the wave absorbing material provided by the present invention are described in detail below with reference to the examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, which are only for further illustrating the features and advantages of the present invention, but not limiting the claims of the present invention, and the scope of protection of the present invention is not limited to the examples described below.
Example 1
Taking carbonyl iron powder, adding a certain amount of ultrapure water, adding a horizontal ball mill, ball milling for 1h to obtain carbonyl iron water solution, mixing and stirring the prepared carbonyl iron water solution and graphene oxide water solution for 2h to obtain precursor solution; carbonyl iron powder: graphene oxide mass ratio is 100:5;
2, adding the precursor solution obtained in the step 1 into a horizontal ball mill, ball milling for 2 hours at a rotating speed of 2000r/min, adding a sand mill, sanding for 8 hours, adding a high-speed shearing emulsifying machine, shearing for 20 minutes at a high speed, and obtaining a mixed solution at a rotating speed of 8000 r/min;
3, solid-liquid separation is carried out on the mixed solution obtained in the step 2 through a cluster type multi-tube filter, the water content of the obtained wet powder is 20%, and the mixed wet powder is dried through a vacuum drying oven to obtain mixed dry powder; the drying temperature is 120 ℃, and the drying time is 4 hours;
and 4, adding the mixed dry powder obtained in the step 3 into a continuous rotary furnace for sintering, wherein the sintering temperature is 280 ℃ (250-350 ℃) and the sintering time is 8 hours, and adding the materials into a superfine material pulverizer in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, and the particle size is 5 mu m.
The graphene oxide/carbonyl iron composite material prepared in example 1 of the present invention was characterized.
Referring to fig. 2, fig. 2 is a scanning electron micrograph of the graphene oxide/carbonyl iron composite material prepared in example 1 of the present invention.
As can be seen from fig. 2, the graphene oxide/carbonyl iron composite material is successfully prepared in this embodiment, the particle size of the graphene oxide/carbonyl iron composite material is about 1-2 μm, and the graphene oxide layer completely coats the surface of the carbonyl iron particle. Further, it was found that small carbonyl iron particles were uniformly dispersed on the surface of the graphene oxide layer by careful observation.
Referring to fig. 3, fig. 3 is a transmission electron micrograph of the graphene oxide/carbonyl iron composite material prepared in example 1 of the present invention.
As can be seen from fig. 3, the graphene oxide/carbonyl iron composite material nanoparticle prepared in this embodiment has a core-shell structure, the core is carbonyl iron nanoparticle, the size of the carbonyl iron nanoparticle is about 30nm, the shell is graphene oxide, the carbonyl iron nanoparticle and graphene oxide have good binding property, and part of carbonyl iron nanoparticle is dispersed on the surface of the graphene oxide sheet layer, so that the carbonyl iron nanoparticle is in a uniformly dispersed state.
Performance detection is performed on the graphene oxide/carbonyl iron composite material prepared in the embodiment 1 of the invention.
The powder product obtained in the embodiment is uniformly mixed with solid paraffin according to the mass ratio of 4:6, and is pressed into a coaxial style with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by a special die, and the wave absorption performance of the coaxial style is tested by an Agilent TE5071C vector network analyzer with the test frequency of 2-18 GHz.
Referring to fig. 4, fig. 4 is a graph showing the wave absorbing performance of a wave absorber prepared from a graphene oxide/carbonyl iron composite material according to an embodiment of the present invention.
As shown in FIG. 4, the test thickness is 1.5mm, the maximum absorption is-48.4 dB at 14.1GHz, the wave absorption is below-10 dB in the frequency band of 11.6-16.8 GHz, and the effective absorption width is 5.2GHz.
Whereas when the test thickness was 2.5mm, the maximum absorption was-32.5 dB at 8.6 GHz.
The graphene oxide/carbonyl iron composite material prepared in the embodiment 1 of the invention is subjected to heat conduction performance detection.
Referring to table 1, table 1 shows the thermal conductivity of the graphene oxide/carbonyl iron composite material prepared in the examples of the present invention.
TABLE 1
| Sample name | Example 1 | Example 2 | Example 3 |
| Coefficient of thermal conductivity (W/m.K) | 2.4 | 3.1 | 2.6 |
Example 2
Taking carbonyl iron powder, adding a certain amount of ultrapure water, adding a horizontal ball mill, ball-milling for 4 hours to obtain carbonyl iron water solution, mixing and stirring the prepared carbonyl iron water solution and graphene oxide water solution for 4 hours to obtain precursor solution; carbonyl iron powder: graphene oxide mass ratio is 100:15;
2, adding the precursor solution obtained in the step 1 into a horizontal ball mill, ball milling for 1h at a rotating speed of 2000r/min, adding a sand mill, sanding for 2h, adding a high-speed shearing emulsifying machine, shearing for 10min at a high speed and at a rotating speed of 8000r/min to obtain a mixed solution;
3, solid-liquid separation is carried out on the mixed solution obtained in the step 2 through a cluster type multi-tube filter, the water content of the obtained wet powder is 15%, and the mixed wet powder is dried through a vacuum drying oven to obtain mixed dry powder; the drying temperature is 150 ℃ and the drying time is 8 hours;
and 4, adding the mixed dry powder obtained in the step 3 into a continuous rotary furnace for sintering, wherein the sintering temperature is 250 ℃, the sintering time is 12 hours, and adding the materials into a superfine material pulverizer in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, wherein the particle size is 15 mu m.
Performance detection is performed on the graphene oxide/carbonyl iron composite material prepared in the embodiment 2 of the invention.
The powder product obtained in the embodiment is uniformly mixed with solid paraffin according to the mass ratio of 4:6, and is pressed into a coaxial style with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by a special die, and the wave absorption performance of the coaxial style is tested by an Agilent TE5071C vector network analyzer with the test frequency of 2-18 GHz.
Referring to fig. 4, fig. 4 is a graph showing the wave absorbing performance of a wave absorber prepared from a graphene oxide/carbonyl iron composite material according to an embodiment of the present invention.
As shown in FIG. 4, when the test thickness is 1.5mm, the maximum absorption is-35.7 dB at 10.8GHz, the wave absorption is below-10 dB in the frequency band of 9.1-12.9 GHz, and the effective absorption width is 3.8GHz.
Whereas when the test thickness was 2.5mm, the maximum absorption reached at 6.4GHz was-26.3 dB.
The graphene oxide/carbonyl iron composite material prepared in the embodiment 2 of the invention is subjected to heat conduction performance detection.
Referring to table 1, table 1 shows the thermal conductivity of the graphene oxide/carbonyl iron composite material prepared in the examples of the present invention.
Example 3
Taking carbonyl iron powder, adding a certain amount of ultrapure water, adding a horizontal ball mill, ball milling for 2 hours to obtain carbonyl iron water solution, mixing and stirring the prepared carbonyl iron water solution and graphene oxide water solution for 2 hours to obtain precursor solution; carbonyl iron powder: graphene oxide mass ratio is 100:5;
2, adding the precursor solution obtained in the step 1 into a horizontal ball mill, ball milling for 2 hours at a rotating speed of 2000r/min, adding a sand mill, sanding for 4 hours, adding a high-speed shearing emulsifying machine, shearing for 30 minutes at a high speed, and obtaining a mixed solution at a rotating speed of 8000 r/min;
3, solid-liquid separation is carried out on the mixed solution obtained in the step 2 through a cluster type multi-tube filter, the water content of the obtained wet powder is 20%, and the mixed wet powder is dried through a vacuum drying oven to obtain mixed dry powder; the drying temperature is 120 ℃, and the drying time is 8 hours;
and 4, adding the mixed dry powder obtained in the step 3 into a continuous rotary furnace for sintering, wherein the sintering temperature is 320 ℃, the sintering time is 6 hours, and adding the materials into a superfine material pulverizer in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, and the particle size is 12 mu m.
Performance detection is performed on the graphene oxide/carbonyl iron composite material prepared in the embodiment 3 of the invention.
The powder product obtained in the embodiment is uniformly mixed with solid paraffin according to the mass ratio of 4:6, and is pressed into a coaxial style with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by a special die, and the wave absorption performance of the coaxial style is tested by an Agilent TE5071C vector network analyzer with the test frequency of 2-18 GHz.
Referring to fig. 4, fig. 4 is a graph showing the wave absorbing performance of a wave absorber prepared from a graphene oxide/carbonyl iron composite material according to an embodiment of the present invention.
As shown in FIG. 4, when the test thickness is 1.5mm, the maximum absorption is-34.8 dB at 6.1GHz, the wave absorption is below-10 dB in the frequency band of 4.2-7.5 GHz, and the effective absorption width is 3.3GHz.
Whereas when the test thickness was 2.5mm, the maximum absorption reached at 4.2GHz was-24.6 dB.
The graphene oxide/carbonyl iron composite material prepared in the embodiment 3 of the invention is subjected to heat conduction performance detection.
Referring to table 1, table 1 shows the thermal conductivity of the graphene oxide/carbonyl iron composite material prepared in the examples of the present invention.
The graphene oxide/carbonyl iron composite wave-absorbing material, the preparation method thereof and the graphene-based wave-absorbing material provided by the invention are described in detail, and specific examples are used herein to illustrate the principles and the implementation modes of the invention, and the description of the examples is only for helping to understand the method and the core ideas of the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and implementing any combined methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (9)
1. The preparation method of the graphene oxide/carbonyl iron composite material is characterized by comprising the following steps of:
a) Premixing carbonyl iron and graphene oxide aqueous solution to obtain a precursor solution;
the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100;
the particle size of the carbonyl iron particles is 0.1-5 mu m;
b) Grinding and homogenizing emulsification are carried out on the precursor solution obtained in the steps, and mixture powder is obtained after post treatment;
c) Sintering the mixture powder obtained in the steps to obtain a graphene oxide/carbonyl iron composite material;
the sintering temperature is 250-350 ℃;
the sintering time is 4-12 hours;
the graphene oxide/carbonyl iron composite material comprises carbonyl iron and a graphene oxide layer compounded on the surface of the carbonyl iron;
the thickness of the graphene oxide layer is 0.3-10 nm;
carbonyl iron particles are further compounded on the surface of the graphene oxide layer;
the graphene oxide/carbonyl iron composite material has a core-shell structure.
2. The preparation method of claim 1, wherein the particle size of the graphene oxide/carbonyl iron composite particles is 0.1-5 μm;
and the particle size of carbonyl iron particles compounded on the surface of the graphene oxide layer is 5-100 nm.
3. The method of claim 1, wherein the carbonyl iron comprises a carbonyl iron aqueous solution;
the mass concentration of the carbonyl molten iron solution is 1% -5%;
the mass concentration of the graphene oxide aqueous solution is 0.05-1%.
4. The method according to claim 3, wherein the carbonyl iron aqueous solution is obtained by pre-ball milling carbonyl iron powder and water;
the pre-ball milling time is 0.5-5 h;
the particle size of the ball milled powder is 2-20 mu m.
5. The method of claim 1, wherein the premixing comprises agitation mixing;
the premixing time is 0.5-2 h.
6. The method of manufacturing according to claim 1, wherein the grinding includes ball milling and sand milling;
the grinding time is 1-15 h;
the homogenizing emulsification comprises high-speed shearing homogenizing emulsification;
the homogenizing and emulsifying time is 10-50 min;
the rotational speed of the homogenizing emulsification is 5000-15000 r/min.
7. The preparation method of claim 6, wherein the ball milling time is 0.5-5 hours;
the rotation speed of the ball milling is 400-800 r/min;
the sanding time is 0.5-10 h;
the rotating speed of the sand grinding is 1500-3000 r/min;
the particle size of the sand grinding medium is 1.2-1.4 mm.
8. The preparation method according to claim 1, wherein the specific steps of the post-treatment are:
filtering the homogenized and emulsified mixed solution to obtain mixed wet powder, and drying to obtain mixed powder;
the filtering comprises bundling filtering;
the water content of the mixed wet powder is 10% -25%;
the drying time is 4-20 hours;
the temperature of the drying is 80-150 ℃.
9. The wave-absorbing material is characterized by comprising the graphene oxide/carbonyl iron composite material prepared by the preparation method according to any one of claims 1-8.
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