CN113621893B - High-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material and preparation method and application thereof - Google Patents
High-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
- H01Q17/004—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems using non-directional dissipative particles, e.g. ferrite powders
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention relates to a high-temperature-resistant flaky iron-cobalt-germanium microwave absorbing material as well as a preparation method and application thereof, belonging to the technical field of wave absorbing materials. The material solves the problems that FeCo alloy has high hardness and is difficult to break, and has high temperature resistance, high low-frequency absorption capacity and thin thickness. Respectively weighing iron particles, cobalt sheets and germanium particles, putting the iron particles, the cobalt sheets and the germanium particles into a vacuum electric arc furnace, fully smelting the iron particles, the cobalt sheets and the germanium particles under the atmosphere of high-purity argon to obtain a block alloy, manually crushing the block alloy, putting the crushed block alloy into a vibration ball mill for ball milling, and filtering and drying the crushed block alloy to obtain a final powder sample. Fe6.5Co3.5GexThe powder has an obvious sheet structure, the Curie temperature is 850.6 ℃, the powder has good microwave absorption performance in the frequency range of 2-18GHz, the maximum reflection loss reaches-14.16 dB when the thickness is 2mm, and the effective bandwidth is 2.7 GHz; the maximum reflection loss reaches-18.40 dB when the thickness is 3 mm.
Description
Technical Field
The invention relates to a high-temperature-resistant wave-absorbing material, a preparation method and application thereof, in particular to a high-temperature-resistant flaky iron-cobalt-germanium wave-absorbing material, belonging to the technical field of wave-absorbing materials.
Background
As is generally known at present, various electronic products have become a new electromagnetic wave radiation source while bringing great convenience to people. A large amount of electromagnetic radiation not only can cause the problem of electromagnetic interference, affect the normal operation of other surrounding electronic equipment, cause unpredictable results, but also seriously affect the health of people. Moreover, stealth technology has also attracted more and more attention from various countries as an effective means for improving the operational efficiency and survival time of weapons. Whether for the purpose of protecting environment and human health, or guaranteeing information safety and national defense safety, research and improvement of wave-absorbing materials, and continuous improvement and improvement of wave-absorbing performance are imperative. The wave-absorbing material is a functional material capable of absorbing and attenuating incident electromagnetic waves and converting the incident electromagnetic waves into other forms of energy to be lost, and mainly comprises a base material and an absorbent, wherein the base material plays a role in bonding and bearing the energy, and the absorbent plays a role in absorbing and attenuating the electromagnetic waves. The wave-absorbing material needs to meet the impedance matching principle and attenuation characteristic for realizing efficient wave absorption, and ideally, when the wave impedance of a medium is equal to that of a free space, electromagnetic waves can completely enter the wave-absorbing material without reflection, so that the optimal impedance matching state is achieved. The loss mechanism of the wave-absorbing material to electromagnetic waves is divided into resistance loss, dielectric loss and magnetic loss, and the electromagnetic waves entering the material are attenuated through various loss mechanisms.
According to the knowledge of the applicant, the existing wave-absorbing material has poor absorption performance or thick thickness in the low-frequency band of the frequency range of 2-18GHz, and meanwhile, the wave-absorbing material has poor wave-absorbing performance at high temperature. The metal micro powder (Fe, Co, Ni) and the alloy thereof are greatly researched as a microwave absorbent due to the characteristics of high saturation magnetization, magnetic permeability and the like of the metal micro powder, the FeCo alloy is used as a material with the highest Curie temperature, has an application prospect of being used as a microwave absorbing material at a high temperature, but has the problems of high hardness and difficulty in crushing, the doping of Ge solves the problem that FeCo is difficult to crush, and the formed sheet structure is favorable for breaking through the Snoek limit, so that the material obtains higher saturation magnetization and magnetic permeability, and the magnetic loss capability of the material is improved.
At present, some researches on FeCo nano-particle/paraffin composite wave-absorbing materials exist, and under low frequency, the prepared material is not in a sheet shape, so that the real part value of the magnetic conductivity is not high, and the thickness of the material is up to 4mm or more when an absorption peak is required to appear at 4 GHz. While relatively few studies have been made on Ge-doped FeCo alloys, among which Fe36Co62Ge2Research on the alloy, wherein the prepared material is 45-micron flaky powder, and the magnetic and mechanical properties of the alloy are researched; with Fe as a new Heusler alloy2CoGe research, and the structure and magnetism of the material are researched. However, in the field of wave-absorbing materials, nearly no research has been made on Ge-doped FeCo alloys.
Disclosure of Invention
The technical problem solved by the invention is as follows: the high-temperature resistant flaky iron-cobalt-germanium wave-absorbing material with excellent wave-absorbing performance, the preparation method and the application thereof are provided, the problems of high hardness and difficulty in breaking of FeCo alloy are solved, and the problems of thicker wave-absorbing coating under low frequency and poor wave-absorbing performance under high temperature are solved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material comprises the following steps:
(1) according to the ratio of stoichiometric numbers of iron, cobalt and germanium in the raw materials of 6.5: 3.5: x, respectively weighing iron particles, cobalt sheets and germanium particles as raw materials, wherein the value of x is 0.2, 0.4, 0.6, 0.8 or 1;
(2) putting the raw materials in the step (1) into a vacuum arc furnace, firstly extracting high vacuum, then introducing high-purity argon as protective gas, repeatedly smelting to ensure that the components are uniform, and cooling to obtain a block alloy;
(3) simply manually crushing the block alloy obtained in the step (2), putting the crushed block alloy into a vibration ball mill for ball milling, and then filtering and drying the crushed block alloy to obtain a powder sample Fe6.5Co3.5Gex。
Preferably, the ratio of the stoichiometric numbers of iron, cobalt and germanium in the wave-absorbing material in the step (1) is 6.5: 3.5: 0.2.
preferably, in the step (1), the purity of the raw materials is 99.9% or more, and the weighing error is within 0.5 mg.
Preferably, in the step (2), the high vacuum degree is 7X 10-4Pa or less.
Preferably, in the step (2), the repeated smelting is performed by turning over after smelting and cooling, and is repeated for 5 times, and each smelting lasts for about 1 minute.
Preferably, in the step (3), the ball milling medium for ball milling is absolute ethyl alcohol.
Preferably, the following components: in the step (3), the ball milling tank for ball milling is made of stainless steel; the ball-milling balls are bearing steel balls; the ball-milling ball-material ratio is 20: 1; the ball milling time is 25 h.
Preferably, the following components: in the step (3), the drying temperature is 70 ℃; the drying time is 5-10 min.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the high-temperature resistant flaky iron-cobalt-germanium wave-absorbing material prepared by any one of the methods.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the high-temperature-resistant flaky iron-cobalt-germanium wave-absorbing material prepared by any method is applied to the field of communication.
The invention leads Fe to be doped by Ge6.5Co3.5GexThe alloy has a sheet structure, breaks through the Snoek limit, improves the saturation magnetization and the magnetic conductivity, enhances the microwave absorption performance, and simultaneously maintains the high Curie temperature.
The invention has the beneficial effects that:
(1) the preparation method has low raw material cost and simple process flow, and the equipment only needs a vacuum arc furnace and a vibration ball mill without other special equipment;
(2) ge-doped sheet Fe of the invention6.5Co3.5GexThe absorbent has the advantages of thin thickness, light weight, high absorption strength, low absorption frequency point and high usable temperature
(3) The invention solves the problems of large hardness and difficult breakage of FeCo alloy by doping Ge, so that Fe6.5Co3.5GexThe alloy has an obvious sheet structure, is beneficial to breaking through the Snoek limit, improves the saturation magnetization and magnetic conductivity of the alloy, enhances the microwave absorption performance, simultaneously keeps high Curie temperature, has the Curie temperature of 850.6 ℃, has good microwave absorption performance in the frequency range of 2-18GHz, has an absorption peak at 5.82GHz when the thickness is 2mm, achieves the maximum reflection loss of-14.16 dB and has the effective bandwidth of 2.7 GHz; and when the thickness is only 3mm, the frequency of the absorption peak is already less than 4GHz, the absorption peak appears at 3.6GHz, and the maximum reflection loss reaches-18.40 dB.
(4) In particular Fe6.5Co3.5Gex(x is 0.2) and a reflection loss of-10 dB or less at a coating thickness of 1.5mm, at 7.The reflection loss reaches-10.80 dB at 92GHz, the effective bandwidth is 2.24GHz (6.92-9.16GHz), and the other x-valued wave-absorbing material of the invention can not reach the absorption effect of-10 dB at 1.5 mm; and at different thicknesses, Fe6.5Co3.5GexThe maximum reflection loss values (x ═ 0.2) are all the largest.
(5) The wave-absorbing material has a certain application prospect in the field of communication, and can be used as a wave-absorbing coating to be coated on the surface of an electronic device, so that the problems of electromagnetic interference and electromagnetic pollution can be solved. Meanwhile, in the technical field of radar stealth, the wave-absorbing material disclosed by the invention has the characteristics of high Curie temperature and strong microwave absorption capacity at low frequency, and is very likely to be applied to scenes with high temperature and frequency bands below 6 GHz.
(6) The wave-absorbing material has the advantages of thinner and lighter coating when used as a wave-absorbing coating because the particle size is only 1-3 mu m.
In conclusion, the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material is obtained by doping Ge, has excellent high-temperature characteristic and microwave absorption characteristic, and has wide application prospect in the field of microwave absorption, particularly as a microwave absorbent in a high-temperature environment.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 shows the wave-absorbing material Fe in examples 2 and 5 of the present invention6.5Co3.5Gex(X ═ 0.4 and 1) X-ray diffraction patterns;
FIG. 2 shows the wave-absorbing material Fe in embodiment 2 of the present invention6.5Co3.5Gex(x ═ 0.4) scanning electron microscope patterns;
FIG. 3 shows the wave-absorbing material Fe in embodiment 5 of the present invention6.5Co3.5Gex(x ═ 1) scanning electron microscope pattern;
FIG. 4 shows the wave-absorbing material Fe in embodiment 5 of the present invention6.5Co3.5Gex(x ═ 1) differential scanning calorimetry patterns;
FIG. 5 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5GexGraph of real part of dielectric constant (x ═ 0.2, 0.4, 0.6, 0.8, 1);
FIG. 6 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) plot of imaginary dielectric constant;
FIG. 7 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5GexGraph of real permeability part of (x ═ 0.2, 0.4, 0.6, 0.8, 1);
FIG. 8 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) plot of imaginary permeability;
FIG. 9 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) microwave reflection loss plot at 1.5mm thickness;
FIG. 10 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) microwave reflection loss plot at thickness 2 mm;
FIG. 11 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) microwave reflection loss plot at 2.5mm thickness;
FIG. 12 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5GexMicrowave reflection loss profile at thickness 3mm of (x ═ 0.2, 0.4, 0.6, 0.8, 1);
fig. 13 is a scanning electron microscope pattern of the wave-absorbing material fe6.5co3.5gex (x ═ 0.4) in example 2 of the present invention;
Detailed Description
Example 1
Ge-doped sheet Fe of this example6.5Co3.5Gex(x ═ 0.2), the preparation method comprises the following steps:
(1) the ratio of the using precision of 0.1mg electron balance according to stoichiometric number is 6.5: 3.5: 0.2, 3.1091g of iron particles (purity 99.9%), 1.7665g of cobalt tablets (purity 99.9%) and 0.1244g of germanium particles (purity 99.9%) were weighed out within an error of 0.5mg as raw materials.
(2) Putting the raw materials in the step (1) into a vacuum electric arc furnace, putting a titanium ingot at the center position, and extracting to 7 multiplied by 10-4Vacuum degree below Pa. Then introducing high-purity argon as protective gas, smelting titanium ingot, and fully absorbing oxygen possibly remaining in the furnace. And then, starting to smelt the alloy, wherein each alloy needs to be turned over after being melted and cooled in order to ensure uniform components, and the process is repeated for 5 times, and each smelting lasts for about 1 minute. And after the block alloy is completely cooled, filling air, opening the furnace door, and taking out the block alloy.
(3) Putting the block alloy taken out in the step (2) into a large steel tank, manually crushing the block alloy into small blocks, putting the small blocks into an 80ml stainless steel ball milling tank, adding bearing steel balls, wherein the ball-to-material ratio is 20: 1, adding absolute ethyl alcohol as a ball milling medium, performing vibration ball milling for 25 hours, filtering, and drying at 70 ℃ for 5-10min to obtain the final absorbent Fe6.5Co3.5Gex(x＝0.2)。
Measurement of electromagnetic parameters and microwave absorption performance: the absorbent of this example was Fe6.5Co3.5Gex(x ═ 0.2) was uniformly mixed with paraffin wax, wherein the filling ratio of the powder sample was 80%, and pressed into a small ring having an outer diameter of 7mm and an inner diameter of 3mm using a custom mold. S parameters of different samples in a frequency range of 2-18GHz are tested by using a vector network analyzer Agilent E836B in combination with a coaxial line method, and electromagnetic parameters of the samples are inverted. According to the transmission line theory, the reflection loss characteristic of the material is calculated in a simulation mode.
Example 2
(1) The ratio of the using precision of 0.1mg electron balance according to stoichiometric number is 6.5: 3.5: 0.4, 3.0337g of iron particles (purity 99.9%), 1.77236g of cobalt tablets (purity 99.9%) and 0.2427g of germanium particles (purity 99.9%) were weighed out within 0.5mg as raw materials.
(2) Putting the raw materials in the step (1) into a vacuum electric arc furnace, putting a titanium ingot at the center position, and extracting to 7 multiplied by 10-4Vacuum degree below Pa. Then introducing high-purity argon as protective gas, smelting titanium ingot, and fully absorbing possible residues in the furnaceOxygen gas (c) of (a). And then, starting to smelt the alloy, wherein each alloy needs to be turned over after being melted and cooled in order to ensure uniform components, and the process is repeated for 5 times, and each smelting lasts for about 1 minute. And after the block alloy is completely cooled, filling air, opening the furnace door, and taking out the block alloy.
(3) Putting the block alloy taken out in the step (2) into a large steel tank, manually crushing the block alloy into small blocks, putting the small blocks into an 80ml stainless steel ball milling tank, adding bearing steel balls, wherein the ball-to-material ratio is 20: 1, adding absolute ethyl alcohol as a ball milling medium, performing vibration ball milling for 25 hours, filtering, and drying at 70 ℃ for 5-10min to obtain the final absorbent Fe6.5Co3.5Gex(x＝0.4)。
Measurement of electromagnetic parameters and microwave absorption performance: the absorbent of this example was Fe6.5Co3.5Gex(x ═ 0.4) was mixed homogeneously with paraffin wax, the filling ratio of the powder sample being 80%, and a small ring having an outer diameter of 7mm and an inner diameter of 3mm was pressed using a custom mold. S parameters of different samples in a frequency range of 2-18GHz are tested by using a vector network analyzer Agilent E836B in combination with a coaxial line method, and electromagnetic parameters of the samples are inverted. According to the transmission line theory, the reflection loss characteristic of the material is calculated in a simulation mode.
Example 3
(1) The ratio of the using precision of 0.1mg electron balance according to stoichiometric number is 6.5: 3.5: 0.6, 2.9618g of iron particles (purity 99.9%), 1.6828g of cobalt tablets (purity 99.9%) and 0.3554g of germanium particles (purity 99.9%) were weighed out within 0.5mg as raw materials.
(2) Putting the raw materials in the step (1) into a vacuum electric arc furnace, putting a titanium ingot at the center position, and extracting to 7 multiplied by 10-4Vacuum degree below Pa. Then introducing high-purity argon as protective gas, smelting titanium ingot, and fully absorbing oxygen possibly remaining in the furnace. And then, starting to smelt the alloy, wherein each alloy needs to be turned over after being melted and cooled in order to ensure uniform components, and the process is repeated for 5 times, and each smelting lasts for about 1 minute. And after the block alloy is completely cooled, filling air, opening the furnace door, and taking out the block alloy.
(3) Will be provided withPutting the block alloy taken out in the step (2) into a large steel tank, manually crushing the block alloy into small blocks, putting the small blocks into an 80ml stainless steel ball milling tank, adding bearing steel balls, wherein the ball-to-material ratio is 20: 1, adding absolute ethyl alcohol as a ball milling medium, performing vibration ball milling for 25 hours, filtering, and drying at 70 ℃ for 5-10min to obtain the final absorbent Fe6.5Co3.5Gex(x＝0.6)。
Measurement of electromagnetic parameters and microwave absorption performance: the absorbent of this example was Fe6.5Co3.5Gex(x ═ 0.6) was uniformly mixed with paraffin wax, wherein the filling ratio of the powder sample was 80%, and pressed into a small ring having an outer diameter of 7mm and an inner diameter of 3mm using a custom mold. S parameters of different samples in a frequency range of 2-18GHz are tested by using a vector network analyzer Agilent E836B in combination with a coaxial line method, and electromagnetic parameters of the samples are inverted. According to the transmission line theory, the reflection loss characteristic of the material is calculated in a simulation mode.
Example 4
(1) The ratio of the using precision of 0.1mg electron balance according to stoichiometric number is 6.5: 3.5: 0.8, 2.8932g of iron particles (purity 99.9%), 1.6438g of cobalt tablets (purity 99.9%) and 0.4630g of germanium particles (purity 99.9%) were weighed out within 0.5mg as raw materials.
(2) Putting the raw materials in the step (1) into a vacuum electric arc furnace, putting a titanium ingot at the center position, and extracting to 7 multiplied by 10-4Vacuum degree below Pa. Then introducing high-purity argon as protective gas, smelting titanium ingot, and fully absorbing oxygen possibly remaining in the furnace. And then, starting to smelt the alloy, wherein each alloy needs to be turned over after being melted and cooled in order to ensure uniform components, and the process is repeated for 5 times, and each smelting lasts for about 1 minute. And after the block alloy is completely cooled, filling air, opening the furnace door, and taking out the block alloy.
(3) Putting the block alloy taken out in the step (2) into a large steel tank, manually crushing the block alloy into small blocks, putting the small blocks into an 80ml stainless steel ball milling tank, adding bearing steel balls, wherein the ball-to-material ratio is 20: adding absolute ethyl alcohol as a ball milling medium, performing vibration ball milling for 25 hours, filtering, and drying at 70 ℃ for 5-10min to obtain the final absorbentFe6.5Co3.5Gex(x＝0.8)。
Measurement of electromagnetic parameters and microwave absorption performance: the absorbent of this example was Fe6.5Co3.5Gex(x ═ 0.8) was mixed homogeneously with paraffin wax, the filling ratio of the powder sample being 80%, and a small ring having an outer diameter of 7mm and an inner diameter of 3mm was pressed using a custom mold. S parameters of different samples in a frequency range of 2-18GHz are tested by using a vector network analyzer Agilent E836B in combination with a coaxial line method, and electromagnetic parameters of the samples are inverted. According to the transmission line theory, the reflection loss characteristic of the material is calculated in a simulation mode.
Example 5
(1) The ratio of the using precision of 0.1mg electron balance according to stoichiometric number is 6.5: 3.5: 2.8278g of iron particles (purity 99.9%), 1.6066g of cobalt tablets (purity 99.9%) and 0.5656g of germanium particles (purity 99.9%) were weighed out within 0.5mg as raw materials.
(2) Putting the raw materials in the step (1) into a vacuum electric arc furnace, putting a titanium ingot at the center position, and extracting to 7 multiplied by 10-4Vacuum degree below Pa. Then introducing high-purity argon as protective gas, smelting titanium ingot, and fully absorbing oxygen possibly remaining in the furnace. And then, starting to smelt the alloy, wherein each alloy needs to be turned over after being melted and cooled in order to ensure uniform components, and the process is repeated for 5 times, and each smelting lasts for about 1 minute. And after the block alloy is completely cooled, filling air, opening the furnace door, and taking out the block alloy.
(3) Putting the block alloy taken out in the step (2) into a large steel tank, manually crushing the block alloy into small blocks, putting the small blocks into an 80ml stainless steel ball milling tank, adding bearing steel balls, wherein the ball-to-material ratio is 20: 1, adding absolute ethyl alcohol as a ball milling medium, performing vibration ball milling for 25 hours, filtering, and drying at 70 ℃ for 5-10min to obtain the final absorbent Fe6.5Co3.5Gex(x＝1)。
Measurement of electromagnetic parameters and microwave absorption performance: the absorbent of this example was Fe6.5Co3.5Gex(x-1) was uniformly mixed with paraffin wax, wherein the filling ratio of the powder sample was 80%, and pressed out using a custom moldA small ring with the diameter of 7mm and the inner diameter of 3 mm. S parameters of different samples in a frequency range of 2-18GHz are tested by using a vector network analyzer Agilent E836B in combination with a coaxial line method, and electromagnetic parameters of the samples are inverted. According to the transmission line theory, the reflection loss characteristic of the material is calculated in a simulation mode.
FIG. 1 shows the wave-absorbing material Fe in examples 2 and 5 of the present invention6.5Co3.5Gex(X ═ 0.4 and 1) X-ray diffraction patterns; as can be seen, the diffraction patterns of the two samples are substantially the same, and each of the two samples has a diffraction peak at 44.74 °, 65.66 ° and 82.42 °, which respectively correspond to the (110), (200) and (211) crystal planes of the FeCo phase, and the results are close to those of PDF # 48-1817. No obvious Ge element related diffraction peak exists in the graph, because Ge enters FeCo crystal lattice to form Fe- (Co, Ge) solid solution with a body-centered cubic (bcc) structure after 25h ball milling, and meanwhile, disordered A2 phase formation is proved by a wide high diffraction peak of 44.74 degrees and weak diffraction peaks of 65.66 degrees and 82.42 degrees.
FIG. 2 shows the wave-absorbing material Fe in embodiment 2 of the present invention6.5Co3.5Gex(x ═ 0.4) scanning electron microscope patterns; as can be seen from the figure, the particles are in the form of platelets, of uniform size, essentially 1-3 μm in size.
FIG. 3 shows the wave-absorbing material Fe in embodiment 5 of the present invention6.5Co3.5Gex(x ═ 1) scanning electron microscope pattern; as can be seen from the figure, the particles are in the form of flakes, and in addition to small particles of 1 to 3 μm, large particles are formed by agglomeration.
FIG. 4 shows the wave-absorbing material Fe in embodiment 5 of the present invention6.5Co3.5Gex(x ═ 1) differential scanning calorimetry patterns; as can be seen from the figure, there is a distinct exothermic peak and an endothermic peak during the sample temperature increase from room temperature to 1000 deg.C, indicating that there are two phase transitions during this process. An obvious exothermic peak exists at 406.6 ℃, and the sample begins to crystallize at the moment, so that an alpha- (Fe, Co) phase is separated out; at 850.8 deg.C, a distinct endothermic peak occurs due to the transition of ferromagnetic α - (Fe, Co) to paramagnetic γ - (Fe, Co), which corresponds to the Curie temperature of the alloy sample. The Curie temperature of the sample is illustrated as 850.8 ℃.
FIG. 5 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5GexGraph of real part of dielectric constant (x ═ 0.2, 0.4, 0.6, 0.8, 1); it can be seen from the figure that the real part of the complex permittivity of the material decreases with increasing frequency except for the sample of example 1, which is favorable for impedance matching of the material at high frequency, but the real part of the complex permittivity of the sample of example 1 is always at a relatively low level, and compared with other samples of examples, the impedance matching characteristic at low frequency is better
FIG. 6 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) plot of imaginary dielectric constant; as can be seen from the figure, the imaginary part of the dielectric constant of example 5 has a plurality of obvious resonance peaks, which are related to the loss of polarization relaxation caused by various polarization phenomena of the sample.
FIG. 7 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5GexGraph of real permeability part of (x ═ 0.2, 0.4, 0.6, 0.8, 1); the real part of permeability of each example sample shows a tendency to decrease with increasing frequency, related to the Snoek limit of the material.
FIG. 8 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) plot of imaginary permeability; it can be seen from the figure that the sample of example 4 has a higher value of the imaginary part of the magnetic permeability at 2-18GHz and thus has a higher magnetic loss capability than the samples of other examples.
FIG. 9 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) microwave reflection loss plot at 1.5mm thickness; as can be seen from the figure, the maximum reflection loss of the sample of example 1 reaches below-10 dB at the thickness of 1.5mm, reaches-10.80 dB at 7.92GHz, and the effective bandwidth is 2.24GHz (6.92-9.16 GHz).
FIG. 10 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x is 0.2, 0.4, 0.6, 0.8, 1) microwave with thickness of 2mmA reflection loss curve graph; as can be seen from the figure, when the thickness of each sample in the embodiment is 2mm, the sample in the embodiment 1 has the best wave absorbing performance compared with the samples in other embodiments, the maximum reflection loss is achieved at 5.82GHz, the maximum reflection loss reaches-14.16 dB, and the effective bandwidth is 2.7GHz (4.64-7.34 GHz).
FIG. 11 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5Gex(x ═ 0.2, 0.4, 0.6, 0.8, 1) microwave reflection loss plot at 2.5mm thickness; as can be seen from the figure, when the thickness of each sample in the embodiment is 2.5mm, the sample in the embodiment 1 has the best wave absorbing capability, the maximum reflection loss reaches-16.58 dB at 4.42GHz when the thickness is 2.5mm, and the effective bandwidth is 2.24GHz (3.56-5.8 GHz).
FIG. 12 shows the wave-absorbing material Fe in examples 1-5 of the present invention6.5Co3.5GexMicrowave reflection loss profile at thickness 3mm of (x ═ 0.2, 0.4, 0.6, 0.8, 1); as can be seen from the figure, when the thickness of the sample of each example is 3mm, the sample of example 1 has the best wave absorbing capability, the maximum reflection loss reaches-18.40 dB at 3.6GHz, and the effective bandwidth is 1.78GHz (2.86-4.64 GHz).
The technical solutions of the present invention are not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the present invention.
Claims (10)
1. A preparation method of a high-temperature-resistant flaky iron-cobalt-germanium wave-absorbing material is characterized by comprising the following steps of: the method comprises the following steps:
(1) according to the ratio of stoichiometric numbers of iron, cobalt and germanium in the raw materials of 6.5: 3.5: x, respectively weighing iron particles, cobalt sheets and germanium particles as raw materials, wherein the value of x is 0.2, 0.4, 0.6, 0.8 or 1;
(2) putting the raw materials in the step (1) into a vacuum arc furnace, firstly extracting high vacuum, then introducing high-purity argon as protective gas, repeatedly smelting to ensure that the components are uniform, and cooling to obtain a block alloy;
(3) simply manually crushing the block alloy obtained in the step (2), putting the crushed block alloy into a vibration ball mill for ball milling, and then carrying out ball millingFiltering and drying to obtain powder sample Fe6.5Co3.5Gex。
2. The preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (1), the ratio of the stoichiometric numbers of the iron, the cobalt and the germanium is 6.5: 3.5: 0.2.
3. the preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (1), the purity of the raw materials is more than 99.9%, and the weighing error is within 0.5 mg.
4. The preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (2), the high vacuum degree is 7X 10-4Pa or less.
5. The preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (2), the repeated smelting is to turn over after smelting and cooling, the repeated smelting is repeated for 5 times, and each smelting lasts for about 1 minute.
6. The preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (3), the ball milling medium of the ball milling is absolute ethyl alcohol.
7. The preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (3), the ball milling tank for ball milling is made of stainless steel; the ball-milling balls are bearing steel balls; the ball-milling ball-material ratio is 20: 1; the ball milling time is 25 h.
8. The preparation method of the high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material according to claim 1, characterized by comprising the following steps: in the step (3), the drying temperature is 70 ℃; the drying time is 5-10 min.
9. The high-temperature-resistant sheet iron-cobalt-germanium wave-absorbing material prepared by the method according to any one of claims 1 to 8.
10. The high-temperature-resistant flaky iron-cobalt-germanium wave-absorbing material prepared by the method according to any one of claims 1 to 8 is applied to the field of communication.
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