CN111320165A - 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 number of oxygen-containing groups exist on the surface of the graphene oxide, the graphene oxide is more favorable for chemical combination with the carbonyl iron, a specific compounding process is further adopted, the graphene oxide is coated on the surface of the carbonyl iron to form a wave absorber structure with a special core-shell structure, the dispersion performance of the graphene oxide and the carbonyl iron is improved, the graphene oxide is not agglomerated, the product is compounded uniformly, the advantages of the two materials are combined more effectively, the graphene oxide/carbonyl iron composite wave-absorbing material has excellent electromagnetic absorption performance, and the graphene oxide/carbonyl iron composite wave-absorbing material has a good application prospect in the field of electromagnetic absorption and is more favorable for application and popularization of industrial large-scale 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 enables the electronic products to be widely popularized, and great convenience is brought to the life of people. Along with the rapid development of microwave and communication technologies, the threat of increasingly severe electromagnetic pollution to the environment and biological safety is increasingly emphasized by people, and is not ignored, and becomes the fourth most pollution following atmospheric pollution, water pollution and noise pollution. The protection and shielding of electromagnetic radiation are generally concerned by the society, so the research and development of the high-efficiency wave-absorbing material become a hotspot of the research in the industry. In addition, the research of the high-efficiency wave-absorbing material has important significance for invisibility of weaponry and improvement of survivability of weapon system. Therefore, it is an important issue for human beings to prepare a novel wave-absorbing material and have excellent electromagnetic wave absorption capability in as wide an electromagnetic wave range as possible.
The graphene is a single-layer carbon atom tightly stacked into a two-dimensional hexagonal honeycomb lattice structure, all carbon atoms are connected in an sp2 hybridization mode, microscopically, a single-layer graphene film is not a two-dimensional flat structure but has a stable micro-wavy single-layer structure on a nanometer scale, and is a unique two-dimensional free-state atomic crystal found at present, macroscopically, the graphene can be warped into zero-dimensional fullerene, rolled into a one-dimensional carbon nanotube or stacked into three-dimensional graphite, and the unique two-dimensional periodic honeycomb lattice structure of the graphene has excellent performance due to the existence of a stable carbon six-membered ring, wherein the thickness of the single-layer graphene is only 0.35nm, the graphene is the lightest and thinnest material known at present, and the electron mobility at room temperature is 2 × 105cm2·V-1·s-1The speed of light, 1/300,the theoretical specific surface area can reach 2630m2·g-1The 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-1Young's modulus exceeds 1100GPa, tensile strength exceeds 130GPa, toughness is very good, and when external mechanical force is applied, carbon atoms can adapt to external force through bending deformation without rearranging the carbon atoms, so that the structure is kept stable. These characteristics make it well suited for use in a variety of disciplines and fields.
Particularly, graphene has a high dielectric constant and can be polarized by an external magnetic field in an electromagnetic field, internal electric dipoles of the graphene are relaxed along with the movement of the electric field, partial electric energy is consumed, the dielectric body is heated, and dielectric loss is easily generated by polarization in the external electromagnetic field. Therefore, the method has wide application prospect in the field of wave-absorbing materials. However, a single graphene sheet layer is easily penetrated by electromagnetic waves and loses electromagnetic wave absorption capability, and meanwhile, a single high dielectric loss causes difficulty in impedance matching. Therefore, by compounding the graphene and other electromagnetic absorption materials, the electromagnetic waves can be prevented from being directly transmitted by the barrier effect between the quantum dot matrixes and the steric hindrance effect after penetrating into the composite material, so that the effect of reducing the frequency of the electromagnetic waves is achieved. But at the same time, the defect that graphene is easy to agglomerate affects the application of graphene in the field of wave-absorbing materials.
Therefore, how to find a suitable graphene composite material has excellent wave-absorbing performance, and can ensure that the graphene material is uniformly dispersed and does not agglomerate, which becomes an important problem to be solved urgently by many industry manufacturers and front-line research and development personnel.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a graphene oxide/carbonyl iron composite material, a preparation method thereof, and a wave-absorbing material, and particularly 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, respectively;
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 μm;
carbonyl iron particles are compounded on the surface of the graphene oxide layer;
the particle size of the 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 a graphene oxide aqueous solution to obtain a precursor solution;
B) grinding and homogenizing and emulsifying the precursor solution obtained in the step, and performing post-treatment to obtain mixture powder;
C) and sintering the mixture powder obtained in the step 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, respectively;
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%.
Preferably, the carbonyl iron aqueous solution is obtained by performing pre-ball milling on 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 pre-mixing comprises stirring and mixing;
the premixing time is 0.5-2 h.
Preferably, the milling comprises ball milling and sand milling;
the grinding time is 1-15 h;
the homogeneous emulsification comprises high-speed shearing homogeneous emulsification;
the homogenizing and emulsifying time is 10-50 min;
the rotation speed of the homogenizing emulsification is 5000-15000 r/min.
Preferably, the ball milling time is 0.5-5 h;
the rotating speed of the ball mill is 400-800 r/min;
the sanding time is 0.5-10 h;
the rotational speed of the sanding is 1500-3000 r/min;
the grain diameter of the sanding medium for sanding is 1.2-1.4 mm.
Preferably, the post-treatment comprises the following specific steps:
filtering the homogenized and emulsified mixed solution to obtain mixed wet powder, and drying to obtain mixture powder;
the filtering comprises cluster filtering;
the water content of the mixed wet powder is 10-25%;
the drying time is 4-20 h;
the drying temperature 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 graphene oxide/carbonyl iron composite material prepared by 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 invention aims at the problem that the graphene material is independently used as a wave-absorbing product, is easy to be penetrated by electromagnetic waves and can cause impedance matching difficulty. The invention provides a graphene oxide/carbonyl iron composite material, carbonyl iron is also a typical magnetic loss material, belongs to a second-generation electromagnetic absorption material, has better electromagnetic absorption performance,
the invention also aims at the problems that the existing graphene/carbonyl iron composite material, such as CN106479433 and the like, uses concentrated hydrochloric acid in the reaction, has certain operation risk, and the ultrasonic mechanical stirring can not effectively compound the two materials; the dispersion problem of graphene in the composite material cannot be effectively solved, and no industrialized technical scheme is realized. And for other graphene/carbonyl iron composite materials, although carbonyl iron powder plays a role in effectively supporting and dispersing graphene sheet layers, the problem of re-agglomeration caused by weak binding force still exists. The method particularly selects the graphene oxide as a research direction, utilizes a large number of oxygen-containing groups (such as hydroxyl, carboxyl, epoxy and the like) on the surface of the graphene oxide, utilizes the oxygen-containing groups on the surface of the graphene oxide as target points combined with the nano material, chemically combines the graphene oxide and carbonyl iron, can delay the direct transmission of electromagnetic waves after the electromagnetic waves penetrate into the composite material and are hindered by the barrier effect between quantum lattices and the steric hindrance effect, and thus has the effect of reducing the frequency of the electromagnetic waves.
Aiming at the problems that a graphene oxide film layer is thin and easy to agglomerate and is difficult to effectively disperse and compound with carbonyl iron, the invention adopts a specific compounding process to obtain the composite material with a special core-shell structure, the graphene oxide is coated on the surface of the carbonyl iron to form the composite material, the dispersion performance of the graphene oxide and the carbonyl iron is 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-absorbing material has excellent electromagnetic absorption performance, has good application prospect in the field of electromagnetic absorption, and can be better served in the fields of military industry, consumer electronics and the like. Meanwhile, the preparation method of the composite material provided by the invention is simple in process, mild in condition, safe and environment-friendly, and more beneficial to application and popularization of industrial mass production.
Experimental results show that the graphene oxide/carbonyl iron composite wave-absorbing material prepared by the invention has excellent electromagnetic absorption performance and heat conduction performance.
Drawings
FIG. 1 is a simplified process flow diagram of a manufacturing process provided by an embodiment of the present invention;
fig. 2 is a scanning electron microscope photograph of the graphene oxide/carbonyl iron composite material prepared in example 1 of the present invention;
fig. 3 is a transmission electron microscope photograph of the graphene oxide/carbonyl iron composite prepared in example 1 of the present invention;
fig. 4 is a wave-absorbing performance curve of a wave-absorbing agent prepared from the graphene oxide/carbonyl iron composite material provided by the embodiment of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the 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 selection and source of parameters of the graphene oxide are not particularly limited, and the graphene oxide can be prepared by conventional methods or purchased commercially according to conventional parameters and sources well known to those skilled in the art, and can be selected and adjusted according to actual application conditions, product requirements and quality requirements, 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.
The present invention is not particularly limited to the composite in principle, and may be defined by a composite known to those skilled in the art, and the specific structure of the graphene oxide/carbonyl iron composite material in the present invention is preferably one or more of coating, supporting, attaching, laminating, depositing and doping, more preferably coating, supporting, attaching, laminating, depositing or doping, and even more preferably coating, that is, the graphene oxide/carbonyl iron composite material in the present invention has a core-shell structure, in which the graphene oxide layer is a shell and the carbonyl iron particles are cores.
In the invention, the ratio of each component in the graphene oxide/carbonyl iron composite material is not particularly limited in principle, and a person skilled in the art can select and adjust the components according to the actual application condition, the product requirement and the quality requirement, in order to better improve the dispersion performance of the graphene oxide and the carbonyl iron, reduce agglomeration, realize uniform compounding and improve the electromagnetic absorption performance of the composite wave-absorbing material, the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100, more preferably (1-15): 100, more preferably (3-12): 100, more preferably (5-10): 100.
the specific structure of the graphene oxide/carbonyl iron composite material is not particularly limited in principle, and a person skilled in the art can select and adjust the structure according to the actual application condition, the product requirement and the quality requirement. 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 a person skilled in the art can select and adjust the specific parameters according to the actual application condition, the product requirements and the quality requirements, in order to better improve the dispersion performance of the graphene oxide and the carbonyl iron, reduce agglomeration, realize uniform compounding and improve the electromagnetic absorption performance of the composite wave-absorbing material, the particle size of the carbonyl iron particles is preferably 0.1-5 μm, more preferably 0.5-4 μm, and more preferably 1-3 μm. The particle size (microscopic particle size) of the graphene oxide/carbonyl iron composite material particles is preferably 0.1-5 μm, more preferably 0.6-4.1 μm, and more preferably 1.1-3.1 μm.
In the graphene oxide/carbonyl iron composite material provided by the above steps of the present invention, carbonyl iron particles, more preferably small carbonyl iron particles (nanoparticles), are further attached to the surface of the graphene oxide, and the carbonyl iron particles may be spherical, granular or irregular; the graphene oxide/carbonyl iron core-shell structure can be independently loaded on a graphene oxide sheet layer, and also can be loaded on the surface of the graphene oxide/carbonyl iron core-shell structure. The carbonyl iron particles compounded on the surface of the graphene oxide layer can be better supported between graphene oxide layers, so that the carbonyl iron particles are more uniformly dispersed, and the graphene oxide is not agglomerated.
The specific parameters of the small carbonyl iron particles are not particularly limited, and a person skilled in the art can select and adjust the small carbonyl iron particles according to the actual application condition, the product requirements and the quality requirements, and the particle size of the small carbonyl iron particles is preferably 5-100 nm, more preferably 15-90 nm, more preferably 35-70 nm, and more preferably 45-60 nm.
According to the graphene oxide/carbonyl iron composite material, the traditional graphene and carbonyl iron composite mode is abandoned, the graphene oxide material is adopted, the combined target is increased, the bonding force between the composite materials is improved, the traditional mode that particles are attached to graphene sheet layers is changed, the core-shell form of a specific coating structure is adopted, and then the carbonyl iron particles on the sheet layers are combined, so that the dispersion performance of the graphene oxide and the carbonyl iron is better improved, the agglomeration of the graphene oxide is reduced, the uniform dispersion of the carbonyl iron is also improved, the electromagnetic absorption performance of the composite wave-absorbing material is improved, and the composite wave-absorbing material has better stability. The composite material provided by the invention realizes the spatial multi-structure composition of carbonyl iron in the graphene oxide sheet layer, adopts graphene oxide, is heat-conducting but non-conducting, has the effect of preventing voltage breakdown, and also has the characteristics of electromagnetic absorption and heat conduction.
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 a graphene oxide aqueous solution to obtain a precursor solution;
B) grinding and homogenizing and emulsifying the precursor solution obtained in the step, and performing post-treatment to obtain mixture powder;
C) and sintering the mixture powder obtained in the step to obtain the graphene oxide/carbonyl iron composite material.
The selection and composition of the raw materials in the preparation method of the graphene oxide/carbonyl iron composite material and the corresponding optimization principle of the invention can correspond to the selection and composition of the raw materials in the graphene oxide/carbonyl iron composite material and the corresponding optimization principle, and are not repeated herein.
According to the invention, firstly, carbonyl iron and a graphene oxide aqueous solution are premixed to obtain a precursor solution.
In the invention, the adding mode and specific parameters of the carbonyl iron are not particularly limited in principle, and a person skilled in the art can select and adjust the carbonyl iron according to the actual production condition, the product requirement and the quality requirement. The mass concentration of the molten carbonyl iron solution in the invention is preferably 1% to 5%, more preferably 1.5% to 4.5%, more preferably 2% to 4%, and more preferably 2.5% to 3.5%.
The specific source of the molten carbonyl iron solution is not particularly limited in principle, and a person skilled in the art can select and adjust the molten carbonyl iron solution according to actual production conditions, product requirements and quality requirements. The time for the pre-ball milling is preferably 0.5-5 h, more preferably 1.5-4 h, and more preferably 2.5-3 h. The particle size of the pre-ball milled carbonyl iron powder in the carbonyl iron aqueous solution is preferably 2-20 μm, more preferably 5-17 μm, more preferably 8-15 μm, and more preferably 10-12 μm.
The graphene oxide has the advantages that the graphene oxide has no special limitation on the parameters, the parameters of the graphene oxide known by a person skilled in the art can be selected and adjusted according to the actual application condition, the composite condition and the product performance, the graphene oxide is used for better improving the dispersion performance of the graphene oxide and carbonyl iron, reducing agglomeration and improving the electromagnetic absorption performance of the composite wave-absorbing material, 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 is preferably 1 to 5, 2 to 4, 1 to 3, and the like, and more preferably, the proportion of the graphene oxide having 5 or less sheets is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more. The sheet diameter of the graphene oxide sheet layer is preferably 7-20 μm, more preferably 10-18 μm, and more preferably 12-15 μm. The specific surface area of the graphene oxide is preferably 400-600 m2(ii)/g, more preferably 420 to 580m2(iv)/g, more preferably 450 to 550m2/g。
The specific parameters of the graphene oxide aqueous solution are not particularly limited in principle, and those skilled in the art can select and adjust the parameters according to actual production conditions, product requirements and quality requirements, and in order to better improve the dispersion performance of graphene oxide and carbonyl iron, reduce agglomeration, achieve uniform compounding and improve the electromagnetic absorption performance of the composite wave-absorbing material, the mass concentration of the graphene oxide aqueous solution is preferably 0.05% o to 1%, more preferably 0.1% o to 5% o, more preferably 0.5% o to 1% o, and more preferably 0.6% o to 0.9% o.
In the invention, the adding proportion of the carbonyl iron and the graphene oxide is not particularly limited in principle, and a person skilled in the art can select and adjust the adding proportion according to the actual application condition, the product requirement and the quality requirement, in order to better improve the dispersion performance of the graphene oxide and the carbonyl iron, reduce agglomeration, realize uniform compounding and improve the electromagnetic absorption performance of the composite wave-absorbing material, the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100, more preferably (1-15): 100, more preferably (3-12): 100, more preferably (5-10): 100.
the pre-mixing mode and parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the pre-mixing mode and parameters according to actual production conditions, product requirements and quality requirements. The pre-mixing time is preferably 0.5-2 h, more preferably 0.8-1.8 h, and more preferably 1.0-1.5 h.
The precursor solution obtained in the step is ground, homogenized and emulsified, and the mixture powder is obtained after post-treatment.
The invention particularly adopts a mechanical treatment mode of grinding and homogeneous emulsification, so that the carbonyl iron and the graphene oxide are uniformly compounded, and the special core-shell structure of the carbonyl iron coated by the graphene oxide is realized. In order to better improve the dispersion performance of the graphene oxide and the carbonyl iron, reduce agglomeration, realize uniform compounding and improve the electromagnetic absorption performance of the composite wave-absorbing material, the grinding is preferably carried out by ball milling and sand milling respectively, and more preferably is carried out by ball milling and sand milling in sequence. The grinding time is preferably 1-15 h, more preferably 3-12 h, and more preferably 5-10 h.
The specific parameters of the ball milling and sanding are not particularly limited in principle, and a person skilled in the art can select and adjust the specific parameters according to actual production conditions, product requirements and quality requirements, the time of the ball milling is preferably 0.5-5 hours, more preferably 1.5-4 hours, and more preferably 2.5-3 hours, in order to better improve the dispersion performance of graphene oxide and carbonyl iron, reduce agglomeration, achieve uniform compounding, and improve the electromagnetic absorption performance of the composite wave-absorbing material. The rotation speed of the ball milling 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 sanding time is preferably 0.5-10 hours, more preferably 2.5-8 hours, and more preferably 4.5-6 hours. The rotational speed of sanding is preferably 1500-3000 r/min, more preferably 1800-2700 r/min, more preferably 2000-2500 r/min. The grain diameter of the sanding medium is preferably 1.2-1.4 mm, more preferably 1.22-1.38 mm, and more preferably 1.25-1.35 mm.
The specific parameters of the homogeneous emulsification are not particularly limited in principle, 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 10-50 min, more preferably 15-45 min, more preferably 20-40 min, and more preferably 25-35 min. The rotation speed of the homogeneous emulsification is preferably 5000-15000 r/min, more preferably 7000-13000 r/min, and more preferably 9000-11000 r/min.
In order to further improve the electromagnetic absorption performance of the composite wave-absorbing material and ensure the dispersion performance and uniform composition of the graphene oxide and the carbonyl iron, and complete and detailed preparation process, the post-treatment steps are preferably as follows:
filtering the homogenized and emulsified mixed solution to obtain mixed wet powder, and drying to obtain mixture powder.
The invention has no special limitation on the filtering mode and parameters in principle, and a person skilled in the art can select and adjust the filtering mode and parameters according to the actual production condition, the product requirement and the quality requirement. The water content of the filtered mixed wet powder is preferably 10-25%, more preferably 12-23%, and more preferably 15-20%.
The drying parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the drying parameters according to actual production conditions, product requirements and quality requirements, the drying temperature is preferably 80-150 ℃, more preferably 90-140 ℃, more preferably 100-130 ℃, and more preferably 110-120 ℃ in order to better improve the dispersion performance of the graphene oxide and the carbonyl iron, reduce agglomeration, ensure uniform compounding and improve the electromagnetic absorption performance of the composite wave-absorbing material.
Finally, sintering the mixture powder obtained in the step to obtain the graphene oxide/carbonyl iron composite material.
The sintering parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the parameters according to actual production conditions, product requirements and quality requirements, so that the dispersion performance of the graphene oxide and the carbonyl iron is better improved, agglomeration is reduced, the composite is uniform, the electromagnetic absorption performance of the composite wave-absorbing material is improved, and the sintering temperature is preferably 250-350 ℃, more preferably 270-330 ℃, and more preferably 290-310 ℃. The sintering time is preferably 4-12 hours, more preferably 5-11 hours, more preferably 6-10 hours, and more preferably 7-9 hours.
In order to further ensure the performance of the product, perfect and refine the process flow, the preparation process can comprise the following specific steps:
adding a certain amount of ultrapure water into carbonyl iron powder, adding the mixture into a horizontal ball mill, carrying out ball milling to obtain a carbonyl iron aqueous solution, and mixing and stirring the prepared carbonyl iron aqueous solution and a graphene oxide aqueous solution to obtain a precursor solution.
Adding the precursor solution obtained in the step 1 into a horizontal ball mill for ball milling, adding into a sand mill for sand milling, and adding into a high-speed shearing emulsifying machine for high-speed shearing emulsification to obtain a mixed solution;
3, performing solid-liquid separation on the mixed solution obtained in the step 2 through a cluster 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 oven 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 sintered material into a superfine material crusher in batches to obtain the graphene oxide/carbonyl iron composite material, wherein the particle size is 5-20 micrometers, can be 8-18 micrometers, and can be 10-15 micrometers.
Referring to fig. 1, fig. 1 is a schematic process flow diagram of a preparation process provided in 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 graphene oxide/carbonyl iron composite material prepared by the preparation method of any one of the technical schemes.
The invention has no special limitation on the specific form and shape of the wave-absorbing material, and the specific form and shape of the wave-absorbing material known by the technicians in the field can be selected and adjusted by the technicians in the field according to the actual production condition, the product requirement and the quality requirement. 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 a combination mode of graphene oxide and carbonyl iron is adopted, a large number of oxygen-containing groups (such as hydroxyl, carboxyl, epoxy and the like) exist on the surface of graphene oxide, the oxygen-containing groups on the surface of the graphene oxide are used as target points combined with a nano material, the graphene oxide and the carbonyl iron are chemically combined, electromagnetic waves can be prevented from directly transmitting through the composite material by barrier effect between quantum lattices and steric hindrance effect, and the effect of reducing the frequency of the electromagnetic waves is achieved.
The invention further adopts a specific composite process to obtain the graphene oxide coated on the surface of the carbonyl iron to form a special wave absorber structure, namely, the graphene oxide is coated on the surface of carbonyl iron to form the composite material with a core-shell structure, and carbonyl iron small particles are loaded on the surface of a graphene oxide lamella to better support the graphene oxide lamella, meanwhile, the carbonyl iron can be compounded better based on the multifunctional group of the graphene oxide as a target point, thereby better improving the dispersion performance of the graphene oxide and the carbonyl iron, ensuring that the graphene oxide is not agglomerated and the product is compounded uniformly, effectively solving the agglomeration problem of the composite material, combining the advantages of the two materials more effectively, so that the graphene oxide/carbonyl iron composite wave-absorbing material has excellent electromagnetic absorption performance, the method has good application prospect in the field of electromagnetic wave absorption, and can better serve the fields of military industry, consumer electronics and the like.
Meanwhile, the traditional ultrasonic mode is abandoned, and the graphene oxide wave absorbing agent is obtained only by mixing the graphene oxide solution and the carbonyl iron solution, then carrying out high-speed shearing emulsification, ball milling and sand grinding, then carrying out solid-liquid separation, and then carrying out 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 invention has excellent electromagnetic absorption performance and heat conduction performance.
For further illustration of the present invention, the following describes in detail a graphene oxide/carbonyl iron composite material, a preparation method thereof, and a wave-absorbing material provided by the present invention with reference to examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, which are only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
1, adding a certain amount of ultrapure water into carbonyl iron powder, adding the mixture into a horizontal ball mill, carrying out ball milling for 1h to obtain a carbonyl iron aqueous solution, and mixing and stirring the prepared carbonyl iron aqueous solution and a graphene oxide aqueous solution for 2h to obtain a precursor solution; carbonyl iron powder: the mass ratio of the graphene oxide is 100: 5;
adding the precursor solution obtained in the step 1 into a horizontal ball mill, performing ball milling for 2 hours at a rotating speed of 2000r/min, adding into a sand mill, performing sand milling for 8 hours, adding into a high-speed shearing emulsifying machine, performing high-speed shearing for 20 minutes at a rotating speed of 8000r/min, and thus obtaining a mixed solution;
3, performing solid-liquid separation on the mixed solution obtained in the step 2 through a cluster multi-tube filter to obtain wet powder with the water content of 20%, and drying the mixed wet powder through a vacuum drying oven to obtain mixed dry powder; the drying temperature is 120 ℃, and the drying time is 4 h;
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 ℃), the sintering time is 8 hours, and adding the materials into a superfine material crusher in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, wherein the particle size is 5 microns.
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 microscope photograph of the graphene oxide/carbonyl iron composite prepared in example 1 of the present invention.
As can be seen from fig. 2, the graphene oxide/carbonyl iron composite material successfully prepared by the embodiment has a particle size of about 1 to 2 μm, and the graphene oxide layer completely covers the surface of the carbonyl iron particle. In addition, by careful observation, it can be seen that small carbonyl iron particles are uniformly dispersed on the surface of the graphene oxide layer.
Referring to fig. 3, fig. 3 is a transmission electron microscope photograph of the graphene oxide/carbonyl iron composite prepared in example 1 of the present invention.
As can be seen from fig. 3, the graphene oxide/carbonyl iron composite nanoparticle prepared in this example has a core-shell structure, the core is a carbonyl iron nanoparticle, the size of the core is about 30nm, the shell is graphene oxide, the binding property between the carbonyl iron nanoparticle and graphene oxide is good, and a part of the small carbonyl iron nanoparticles are dispersed on the surface of the graphene oxide sheet layer and are in a uniformly dispersed state.
The performance of the graphene oxide/carbonyl iron composite material prepared in the embodiment 1 of the invention is detected.
The powder product obtained in the embodiment is uniformly mixed with solid paraffin according to the mass ratio of 4:6, the mixture is pressed into a coaxial type with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by using a special mould, and the wave absorbing performance is tested by using an Agilent TE5071C vector network analyzer, wherein the testing frequency is 2-18 GHz.
Referring to fig. 4, fig. 4 is a wave-absorbing performance curve of a wave-absorbing agent prepared from the graphene oxide/carbonyl iron composite material provided by the embodiment of the 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 at the frequency band of 11.6-16.8 GHz, and the effective absorption width is 5.2 GHz.
Whereas, when the test thickness was 2.5mm, the maximum absorption was reached at 8.6GHz as-32.5 dB.
The thermal conductivity of the graphene oxide/carbonyl iron composite material prepared in the embodiment 1 of the invention is detected.
Referring to table 1, table 1 shows thermal conductivity of the graphene oxide/carbonyl iron composite material prepared according to the embodiment 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
1, adding a certain amount of ultrapure water into carbonyl iron powder, adding the mixture into a horizontal ball mill, carrying out ball milling for 4 hours to obtain a carbonyl iron aqueous solution, and mixing and stirring the prepared carbonyl iron aqueous solution and a graphene oxide aqueous solution for 4 hours to obtain a precursor solution; carbonyl iron powder: the mass ratio of the graphene oxide is 100: 15;
adding the precursor solution obtained in the step 1 into a horizontal ball mill, performing ball milling for 1h at the rotating speed of 2000r/min, adding into a sand mill, performing sand milling for 2h, adding into a high-speed shearing emulsifying machine, performing high-speed shearing for 10min at the rotating speed of 8000r/min to obtain a mixed solution;
3, performing solid-liquid separation on the mixed solution obtained in the step 2 through a cluster multi-tube filter to obtain wet powder with the water content of 15%, and drying the mixed wet powder through a vacuum drying oven to obtain mixed dry powder; the drying temperature is 150 ℃, and the drying time is 8 h;
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 crusher in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, wherein the particle size is 15 microns.
The performance of the graphene oxide/carbonyl iron composite material prepared in embodiment 2 of the invention is detected.
The powder product obtained in the embodiment is uniformly mixed with solid paraffin according to the mass ratio of 4:6, the mixture is pressed into a coaxial type with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by using a special mould, and the wave absorbing performance is tested by using an Agilent TE5071C vector network analyzer, wherein the testing frequency is 2-18 GHz.
Referring to fig. 4, fig. 4 is a wave-absorbing performance curve of a wave-absorbing agent prepared from the graphene oxide/carbonyl iron composite material provided by the embodiment of the 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 at the frequency band of 9.1-12.9 GHz, and the effective absorption width is 3.8 GHz.
Whereas, when the test thickness was 2.5mm, the maximum absorption was-26.3 dB at 6.4 GHz.
The thermal conductivity of the graphene oxide/carbonyl iron composite material prepared in embodiment 2 of the invention is detected.
Referring to table 1, table 1 shows thermal conductivity of the graphene oxide/carbonyl iron composite material prepared according to the embodiment of the present invention.
Example 3
1, adding a certain amount of ultrapure water into carbonyl iron powder, adding the mixture into a horizontal ball mill, carrying out ball milling for 2 hours to obtain a carbonyl iron aqueous solution, and mixing and stirring the prepared carbonyl iron aqueous solution and a graphene oxide aqueous solution for 2 hours to obtain a precursor solution; carbonyl iron powder: the mass ratio of the graphene oxide is 100: 5;
adding the precursor solution obtained in the step 1 into a horizontal ball mill, performing ball milling for 2 hours at a rotating speed of 2000r/min, adding into a sand mill, performing sand milling for 4 hours, adding into a high-speed shearing emulsifying machine, performing high-speed shearing for 30 minutes at a rotating speed of 8000r/min, and thus obtaining a mixed solution;
3, performing solid-liquid separation on the mixed solution obtained in the step 2 through a cluster multi-tube filter to obtain wet powder with the water content of 20%, and drying the mixed wet powder through a vacuum drying oven to obtain mixed dry powder; the drying temperature is 120 ℃, and the drying time is 8 h;
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 crusher in batches after sintering to obtain the graphene oxide/carbonyl iron composite material, wherein the particle size is 12 microns.
The performance of the graphene oxide/carbonyl iron composite material prepared in embodiment 3 of the invention is detected.
The powder product obtained in the embodiment is uniformly mixed with solid paraffin according to the mass ratio of 4:6, the mixture is pressed into a coaxial type with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by using a special mould, and the wave absorbing performance is tested by using an Agilent TE5071C vector network analyzer, wherein the testing frequency is 2-18 GHz.
Referring to fig. 4, fig. 4 is a wave-absorbing performance curve of a wave-absorbing agent prepared from the graphene oxide/carbonyl iron composite material provided by the embodiment of the 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 at the frequency band of 4.2-7.5 GHz, and the effective absorption width is 3.3 GHz.
Whereas, when the test thickness was 2.5mm, the maximum absorption was-24.6 dB at 4.2 GHz.
The thermal conductivity of the graphene oxide/carbonyl iron composite material prepared in embodiment 3 of the invention is detected.
Referring to table 1, table 1 shows thermal conductivity of the graphene oxide/carbonyl iron composite material prepared according to the embodiment 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 applied in the description to explain the principle and the implementation manner of the invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 languages of the claims.
Claims (10)
1. The graphene oxide/carbonyl iron composite material is characterized by comprising 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.
2. The graphene oxide/carbonyl iron composite material according to claim 1, wherein the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100, respectively;
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.
3. The graphene oxide/carbonyl iron composite material according to claim 1, wherein the particle size of the graphene oxide/carbonyl iron composite material particles is 0.1 to 5 μm;
carbonyl iron particles are compounded on the surface of the graphene oxide layer;
the particle size of the carbonyl iron particles compounded on the surface of the graphene oxide layer is 5-100 nm.
4. The preparation method of the graphene oxide/carbonyl iron composite material is characterized by comprising the following steps:
A) premixing carbonyl iron and a graphene oxide aqueous solution to obtain a precursor solution;
B) grinding and homogenizing and emulsifying the precursor solution obtained in the step, and performing post-treatment to obtain mixture powder;
C) and sintering the mixture powder obtained in the step to obtain the graphene oxide/carbonyl iron composite material.
5. The preparation method according to claim 4, wherein the mass ratio of the graphene oxide to the carbonyl iron is (0.5-20): 100, respectively;
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%.
6. The preparation method of claim 5, wherein the aqueous solution of the carbonyl iron 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 pre-mixing comprises stirring and mixing;
the premixing time is 0.5-2 h.
7. The method of claim 4, wherein the milling comprises ball milling and sand milling;
the grinding time is 1-15 h;
the homogeneous emulsification comprises high-speed shearing homogeneous emulsification;
the homogenizing and emulsifying time is 10-50 min;
the rotation speed of the homogenizing emulsification is 5000-15000 r/min.
8. The preparation method of claim 7, wherein the ball milling time is 0.5-5 h;
the rotating speed of the ball mill is 400-800 r/min;
the sanding time is 0.5-10 h;
the rotational speed of the sanding is 1500-3000 r/min;
the grain diameter of the sanding medium for sanding is 1.2-1.4 mm.
9. The preparation method according to claim 4, wherein the post-treatment comprises the following specific steps:
filtering the homogenized and emulsified mixed solution to obtain mixed wet powder, and drying to obtain mixture powder;
the filtering comprises cluster filtering;
the water content of the mixed wet powder is 10-25%;
the drying time is 4-20 h;
the drying temperature is 80-150 ℃;
the sintering temperature is 250-350 ℃;
the sintering time is 4-12 h.
10. A wave-absorbing material, which is characterized by comprising the graphene oxide/carbonyl iron composite material according to any one of claims 1 to 3 or the graphene oxide/carbonyl iron composite material prepared by the preparation method according to any one of claims 4 to 9.
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