CN115537684B - Novel iron-based amorphous nanocrystalline wave-absorbing material and preparation method thereof - Google Patents
Novel iron-based amorphous nanocrystalline wave-absorbing material and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 409
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 202
- 239000011358 absorbing material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000003723 Smelting Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000889 atomisation Methods 0.000 claims abstract description 21
- 230000006698 induction Effects 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 131
- 229910045601 alloy Inorganic materials 0.000 claims description 62
- 239000000956 alloy Substances 0.000 claims description 62
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910000831 Steel Inorganic materials 0.000 claims description 40
- 239000010959 steel Substances 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 34
- 229910052804 chromium Inorganic materials 0.000 claims description 28
- 239000011651 chromium Substances 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 28
- 230000002745 absorbent Effects 0.000 claims description 25
- 239000002250 absorbent Substances 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002861 polymer material Substances 0.000 claims description 18
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 229910052758 niobium Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001238 wet grinding Methods 0.000 claims description 14
- 241000251468 Actinopterygii Species 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910000592 Ferroniobium Inorganic materials 0.000 claims description 13
- 229910000805 Pig iron Inorganic materials 0.000 claims description 13
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 claims description 13
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000011810 insulating material Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 238000000137 annealing Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000006096 absorbing agent Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 29
- 230000005291 magnetic effect Effects 0.000 description 9
- XEQZXHPGUAHHPE-UHFFFAOYSA-N [Mn].[Ca].[Si] Chemical compound [Mn].[Ca].[Si] XEQZXHPGUAHHPE-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000003825 pressing Methods 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001808 coupling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000005350 ferromagnetic resonance Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Powder Metallurgy (AREA)
- Soft Magnetic Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a novel iron-based amorphous nanocrystalline wave absorbing material and a preparation method thereof, belonging to the technical field of wave absorbing materials. The beneficial effects of the invention are as follows: the invention adopts the medium-frequency induction smelting and the ultrahigh-pressure water vapor combined atomization, and is matched with the processes of later mechanical ball milling, crystallization annealing treatment and the like to prepare the wave-absorbing material, and the wave-absorbing material has the characteristics of simple process, strong operability and good repeatability, and the prepared iron-based amorphous nanocrystalline wave-absorbing material has the characteristics of strong absorption performance, wide applicable frequency band and thin thickness, has great development potential in the application of high-frequency electromagnetic wave absorbers, and has better application prospect.
Description
The invention relates to a patent application, namely a divisional application of Chinese patent application number 202111331137.1, the application number of the original application is 202111331137.1, the application date is 2021, 11 months and 11 days, and the invention is an iron-based amorphous nanocrystalline wave absorbing material and a preparation method thereof.
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a novel iron-based amorphous nanocrystalline wave-absorbing material and a preparation method thereof.
Background
In recent years, with the rapid development of electronic informatization technology, various electric appliances and electronic devices have been popularized, and electromagnetic wave pollution has been greatly increased. In the field of military, the role and the position of the wave absorbing material in increasingly important stealth and electromagnetic compatibility (EMC) technology are very outstanding, the wave absorbing material becomes a forensic and secret weapon for electronic countermeasure in modern military, and the wave absorbing material is coated on various weaponry and military facilities such as airplanes, tanks, ships, warehouses and the like, so that the wave absorbing material can absorb the reconnaissance electric waves, attenuate reflected signals and reduce the attack of infrared guidance and laser weapons on a weapon system. Meanwhile, the method breaks through the defense area of the enemy radar, which is a powerful means of anti-radar reconnaissance.
By a wave-absorbing material is meant that electromagnetic wave energy incident on the surface of the material is converted into other forms of energy by dielectric loss of the material. The wave-absorbing material is generally formed by compounding a matrix material and a dielectric material through a certain process. The excellent wave-absorbing material must have two basic characteristics, one being a wave impedance matching characteristic and the other being an absorbing characteristic. When the wave-absorbing material is developed, the electromagnetic parameters of the material should be as high as possible to meet the matching conditions, and the imaginary part of the electromagnetic parameters of the material should be as high as possible. The good wave-absorbing material is necessarily a magnetic loss material and is also a dielectric loss material, which provides a basic basis for the selection of materials.
The metal alloy superfine powder has great advantages as a wave absorbing material, the magnetic spectrum of the metal soft magnetic material in the microwave section mainly depends on skin effect and natural resonance, and the resonance frequency of the metal soft magnetic material can be enabled to be more than 2GHz by adjusting the property of the magnetic alloy, so that the complex permeability of the metal soft magnetic material still keeps a larger value in a wide enough frequency band. The high magnetic permeability is especially the imaginary part of complex magnetic permeability, which is beneficial to the design and preparation of the wave-absorbing material, and the sheet system is also beneficial to improving the wave-absorbing performance of the material. At present, most of the wave-absorbing materials are prepared by adopting amorphous materials or nanocrystalline materials as dielectric materials, but the wave-absorbing materials are rarely prepared by adopting amorphous nanocrystalline powder materials, so that the construction of the amorphous nanocrystalline wave-absorbing materials is very significant for developing novel wave-absorbing materials.
In view of this, the present inventors have conducted intensive studies on the above problems, and have produced the present invention.
Disclosure of Invention
The invention aims to provide a novel iron-based amorphous nanocrystalline wave-absorbing material and a preparation method thereof. The preparation method not only improves impedance matching, maintains or improves magnetic loss capacity, but also effectively inhibits skin effect, so that the wave-absorbing material has better wave-absorbing performance in a wider frequency range, and industrial demonstration is expected to be provided for large-scale production of the iron-based amorphous nanocrystalline wave-absorbing material.
In order to achieve the above purpose, the technical scheme adopted by the invention is to provide a novel iron-based amorphous nanocrystalline wave absorbing material, which comprises an iron-based amorphous nanocrystalline alloy, wherein the iron-based amorphous nanocrystalline alloy is of an amorphous/nanocrystalline composite biphase structure, and the iron-based amorphous nanocrystalline alloy is used as an absorbent.
Preferably, the absorbent comprises the following element components in percentage by mass: 6-9% Si,2.0-3.5% B,6-8% Cr,1-3% Cu,4-7% Nb,0.4-0.8% Mo,0.3-0.6% W,0.5-0.75% C,75-79.8% Fe.
Preferably, the absorbent comprises the following element components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe.
Preferably, the appearance of the iron-based amorphous nanocrystalline alloy is fish scale.
Preferably, the alloy further comprises a thermoplastic elastomer high polymer material, wherein the mass ratio of the thermoplastic elastomer high polymer material to the iron-based amorphous nanocrystalline alloy is 2:8.
The invention also provides a preparation method of the novel iron-based amorphous nanocrystalline wave-absorbing material, which adopts medium-frequency induction smelting and ultrahigh-pressure water vapor combined atomization to prepare iron-based amorphous alloy powder; then, carrying out mechanical ball milling treatment on the prepared iron-based amorphous alloy powder; and then high-temperature annealing is carried out to complete the transformation from the amorphous state of the iron-based amorphous alloy powder to the amorphous/nanocrystalline composite dual-phase structure, and the iron-based amorphous nanocrystalline wave-absorbing material is prepared through compositing, and specifically comprises the following steps:
step one, preparing iron-based amorphous alloy powder: selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, and performing medium-frequency induction smelting, ultrahigh-pressure water vapor combined atomization, vacuum drying, screening and batch mixing treatment on the raw materials to obtain iron-based amorphous alloy powder with the grain diameter of D50 of 3-6 mu m;
preparing iron-based amorphous powder: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein the D10 is 5-8 mu m or the D50 is 13-18 mu m or the D90 is 30-35 mu m;
preparing the iron-based amorphous nanocrystalline alloy: the iron-based amorphous powder obtained in the second step is firstly dried for 2-3 hours at the temperature of 90-130 ℃, then is heated to 520-550 ℃ under the protection of inert gas atmosphere, is insulated for 2 hours, and finally is cooled to room temperature to obtain the iron-based amorphous nanocrystalline alloy, wherein the iron-based amorphous nanocrystalline alloy is used as an absorbent.
Preferably, the method further comprises a step four of fully mixing the iron-based amorphous nanocrystalline alloy with a matrix material according to the ratio of 8:2, and then compounding to obtain the iron-based amorphous nanocrystalline wave absorbing material.
Preferably, in the first step, the iron-based amorphous alloy powder comprises the following components in percentage by mass: 6-9% Si,2.0-3.5% B,6-8% Cr,1-3% Cu,4-7% Nb,0.4-0.8% Mo,0.3-0.6% W,0.5-0.75% C,75-79.8% Fe; the material is prepared according to the iron-based amorphous alloy powder components, and industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron are selected as raw materials.
Preferably, in the first step, the smelting power of medium frequency induction smelting is controlled to be 300-500KW, the smelting duration is 60.0-80.0 minutes, when the temperature of molten steel reaches 1500-1520 ℃, the power is reduced to be 100-150KW, 0.8kg of Si-Ca-Mn and 1kg of lime are adopted to carry out slag-making deoxidation treatment on the molten steel, the process duration is 10.0-15.0 minutes, and then slag skimming is clean, and steel casting is carried out;
in the first step, the ultrahigh-pressure water vapor combined atomization adopts nitrogen as a process protective atmosphere, and the flow of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 3.0-4.0mm, the atomizing pressure is 90-120MPa, and the atomizing water flow is 140-190L/min;
drying the iron-based amorphous alloy powder by adopting a vacuum drying oven, wherein the drying temperature is 130-190 ℃, and the vacuum degree is less than or equal to-0.09 MPa;
drying the iron-based amorphous alloy powder by adopting a vacuum drying oven, wherein the drying temperature is 120 ℃, and the vacuum degree is less than or equal to-0.09 MPa;
powder granularity and distribution are controlled by adopting air current classification, and powder laser granularity D50 is controlled: 3-6 μm.
Preferably, in the second step, the ball milling speed of the high-energy ball mill is 200rpm-400rpm, the protective medium is ethanol, and the wet milling time is 40-60h.
Preferably, in the third step, the amorphous powder crystallization annealing treatment is performed by using a vacuum tube furnace: the amorphous powder is brought to a predetermined temperature 520-550 ℃ (this temperature is higher than the initial crystallization temperature T) X1 And lower than the second crystallization temperature T X2 And slightly higher than T X1 Wherein T is X1 ＝515℃，T X2 Heat preservation is carried out for 1-3 hours at the preset temperature, the powder is converted from an amorphous state to an amorphous/nanocrystalline composite double-phase structure, and then furnace cooling or air cooling is carried out, so that the iron-based amorphous nanocrystalline alloy is obtained.
Preferably, in the fourth step, the matrix material is a thermoplastic elastomer polymer material.
Preferably, the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent molten thermoplastic elastomer polymer material are fully mixed according to the ratio of 8:2, and then pressed into a coaxial sample with the outer diameter of 7.0 multiplied by 3.0 multiplied by 1.0-2.0 mm. Through detection, the effective absorption bandwidth delta f of the sample RL <-10dB max up to 6.9GHz, and not lower than 2.7GHz, corresponding to RL when d=1.0 mm min Can reach-15.14 dB at 8.05GHz, can cover the whole x wave band (8-12 GHz), and has excellent high-frequency wave absorbing performance.
Preferably, the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
The technical scheme of the invention has the beneficial effects that:
1. the invention adopts the medium-frequency induction smelting and the ultrahigh-pressure water vapor combined atomization, and is matched with the processes of later mechanical ball milling, crystallization annealing treatment and the like to prepare the wave-absorbing material, and the wave-absorbing material has the characteristics of simple process, strong operability and good repeatability, and the prepared iron-based amorphous nanocrystalline wave-absorbing material has the characteristics of strong absorption performance, wide applicable frequency band and thin thickness, has great development potential in the application of high-frequency electromagnetic wave absorbers, and has better application prospect.
2. The primary particle size D50 of the iron-based amorphous alloy powder prepared by the invention is only 3-6 mu m, and the iron-based amorphous alloy powder is used as an electromagnetic wave absorbing material, and the smaller particle size has higher magnetic permeability and small dielectric constant and is suitable for a higher frequency range; the smaller the particle size of the powder particles, the larger the specific surface area, the larger the contact resistance in the composite material matrix, and the lower the dielectric constant; meanwhile, the smaller and denser the particles are, the higher the filling degree of the wave-absorbing material is, and the permeability of the wave-absorbing material is improved in a same ratio.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a metal powder prepared by the combined atomization of water vapor obtained in accordance with the present invention;
FIG. 2 is an SEM image of the mechanically ball-milled iron-based amorphous powder of the present invention;
FIG. 3 is an XRD pattern of the crystallized annealed iron-based amorphous nanocrystalline alloy obtained in the present invention;
fig. 4 is a simulation graph of the wave absorbing performance of the obtained iron-based amorphous nanocrystalline and thermoplastic elastomer polymer material mixed at different frequencies with a mass percentage of 80%.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
The embodiment provides a novel iron-based amorphous nanocrystalline wave absorbing material, which comprises an iron-based amorphous nanocrystalline alloy, wherein the iron-based amorphous nanocrystalline alloy is of an amorphous/nanocrystalline composite dual-phase structure, and the iron-based amorphous nanocrystalline alloy is used as an absorbent.
As a preferred embodiment, the absorbent comprises the following element components in percentage by mass: 6-9% Si,2.0-3.5% B,6-8% Cr,1-3% Cu,4-7% Nb,0.4-0.8% Mo,0.3-0.6% W,0.5-0.75% C,75-79.8% Fe.
As a preferred embodiment, the absorbent comprises the following element components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe.
As a preferred embodiment, the morphology of the iron-based amorphous nanocrystalline alloy is fish scale.
As a preferred embodiment, the alloy further comprises a thermoplastic elastomer polymer material, wherein the mass ratio of the thermoplastic elastomer polymer material to the iron-based amorphous nanocrystalline alloy is 2:8.
The embodiment also provides a preparation method of the novel iron-based amorphous nanocrystalline wave-absorbing material, which adopts medium-frequency induction smelting and ultrahigh-pressure water vapor combined atomization to prepare iron-based amorphous alloy powder, namely FeSiBCrCuNbMoWC powder; then, carrying out mechanical ball milling treatment on the prepared iron-based amorphous alloy powder; and then high-temperature annealing is carried out to finish the transformation from the amorphous state of the iron-based amorphous alloy powder to the amorphous/nanocrystalline composite dual-phase structure, and the iron-based amorphous nanocrystalline wave-absorbing material is prepared by compounding, and the prepared iron-based amorphous nanocrystalline wave-absorbing material has the characteristics of strong absorption performance, wide applicable frequency band and thin thickness, and specifically comprises the following steps:
step one, preparing iron-based amorphous alloy powder: selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, and performing medium-frequency induction smelting, ultrahigh-pressure water vapor combined atomization, vacuum drying, screening and batch mixing treatment on the raw materials to obtain iron-based amorphous alloy powder with the grain diameter of D50 of 3-6 mu m;
preparing iron-based amorphous powder: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein the D10 is 5-8 mu m or the D50 is 13-18 mu m or the D90 is 30-35 mu m;
preparing the iron-based amorphous nanocrystalline alloy: the iron-based amorphous powder obtained in the second step is firstly dried for 2-3 hours at the temperature of 90-130 ℃, then is heated to 520-550 ℃ under the protection of inert gas atmosphere, is kept for 2 hours, and is finally cooled to room temperature to obtain iron-based amorphous nanocrystalline alloy, wherein the iron-based amorphous nanocrystalline alloy is used as an absorbent;
as a preferred implementation mode, the method further comprises a step four of fully mixing the iron-based amorphous nanocrystalline alloy with a matrix material according to the ratio of 8:2, and then compounding to obtain the iron-based amorphous nanocrystalline wave-absorbing material.
In a preferred embodiment, in the first step, the iron-based amorphous alloy powder comprises the following components in percentage by mass: 6-9% Si,2.0-3.5% B,6-8% Cr,1-3% Cu,4-7% Nb,0.4-0.8% Mo,0.3-0.6% W,0.5-0.75% C,75-79.8% Fe; the material is prepared according to the iron-based amorphous alloy powder components, and industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron are selected as raw materials.
In the first step, the smelting power of medium frequency induction smelting is controlled to be 300-500KW, the smelting time is controlled to be 60.0-80.0 minutes, when the temperature of molten steel reaches 1500-1520 ℃, the power is reduced to be 100-150KW, 0.8kg of Si-Ca-Mn and 1kg of lime are adopted to carry out slag-making deoxidation treatment on the molten steel, the process time is controlled to be 10.0-15.0 minutes, slag skimming is then clean, and steel casting is carried out;
in the first step, the ultrahigh-pressure water vapor combined atomization adopts nitrogen as a process protective atmosphere, and the flow of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 3.0-4.0mm, the atomizing pressure is 90-120MPa, and the atomizing water flow is 140-190L/min;
drying the iron-based amorphous alloy powder by adopting a vacuum drying oven, wherein the drying temperature is 130-190 ℃, and the vacuum degree is less than or equal to-0.09 MPa;
drying the iron-based amorphous alloy powder by adopting a vacuum drying oven, wherein the drying temperature is 120 ℃, and the vacuum degree is less than or equal to-0.09 MPa;
powder granularity and distribution are controlled by adopting air current classification, and powder laser granularity D50 is controlled: 3-6 μm.
As a preferred embodiment, in the second step, the ball milling speed of the high-energy ball mill is 200rpm-400rpm, the protective medium is ethanol, and the wet milling time is 40-60h.
As a preferred embodiment, in the third step, the amorphous powder crystallization annealing treatment is performed using a vacuum tube furnace: the amorphous powder is brought to a predetermined temperature 520-550 ℃ (this temperature is higher than the initial crystallization temperature T) X1 And lower than the second crystallization temperature T X2 And slightly higher than T X1 Wherein T is X1 ＝515℃，T X2 Heat preservation is carried out for 1-3 hours at the preset temperature, the powder is converted from an amorphous state to an amorphous/nanocrystalline composite double-phase structure, and then furnace cooling or air cooling is carried out, so that the iron-based amorphous nanocrystalline alloy is obtained.
In a preferred embodiment, in the fourth step, the base material is a thermoplastic elastomer polymer material.
As a preferred oneIn the embodiment, the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent molten thermoplastic elastomer polymer material are fully mixed according to the ratio of 8:2, and then the mixture is pressed into a coaxial sample with the outer diameter of 7.0 multiplied by 3.0 multiplied by 1.0-2.0 mm. Through detection, the effective absorption bandwidth delta f of the sample RL <-10dB max up to 6.9GHz, and not lower than 2.7GHz, corresponding to RL when d=1.0 mm min Can reach-15.14 dB at 8.05GHz, can cover the whole x wave band (8-12 GHz), and has excellent high-frequency wave absorbing performance. The electromagnetic wave transparency refers to no absorption of electromagnetic waves and transparency.
As a preferred embodiment, the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
The fine nanocrystalline grains in the iron-based amorphous nanocrystalline alloy prepared by the embodiment are distributed on the amorphous matrix, so that the iron-based amorphous nanocrystalline alloy shows better comprehensive performance, and on one hand, the iron-based amorphous nanocrystalline alloy has the characteristic of small atomic density near the surface of amorphous powder, so that the material shows excellent properties such as sound, light, electricity, magnetism, thermodynamics and the like; on the other hand, due to the super exchange coupling effect among the nano-crystalline particles, the soft magnetic material has high initial magnetic conductivity and is inversely proportional to the 6 th power of the grain size, the high magnetic conductivity promotes the input wave impedance at the interface of the wave absorber to be similar to the intrinsic wave impedance of the free space as much as possible, the maximum level of electromagnetic waves is ensured to enter the wave absorber, the reflectivity of the outer interface is reduced, and the impedance matching is facilitated. In addition, the small interface component of the nano particle size occupies a large proportion, unsaturated bonds and dangling bonds are more, and the existence of a large number of dangling bonds leads to interface polarization and the absorption band to be widened. And secondly, the resistivity of the material is greatly improved due to the ultra-fine crystal grains and lattice defects, so that the material is beneficial to improving the microwave permeability and reducing the dielectric constant of the material, and the ferromagnetic resonance and microwave absorption performance of the material are improved. In summary, the iron-based amorphous nanocrystalline absorbing material prepared in the embodiment has strong absorbing performance and excellent broadband and high-frequency absorbing performance.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Embodiment one:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the embodiment comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 70 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 10 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 4.0mm, the atomizing pressure is 110MPa, and the atomizing water flow is 160L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 60 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein D10 is 5-8 mu m or D50 is 13-18 mu m or D90 is 30-35 mu m;
step three: preparing iron-based amorphous nanocrystalline wave absorbing powder: drying the iron-based amorphous powder obtained in the second step at 120 ℃ for 2.5 hours, heating to 530 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, and finally completing the transformation from amorphous state to amorphous/nanocrystalline composite biphase structure, and then carrying out furnace cooling or air cooling to obtain the iron-based amorphous nanocrystalline alloy with the alpha-Fe (Si) nanocrystalline grain size of about 15 nm;
step four: fully mixing the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent fused thermoplastic elastomer polymer material according to the ratio of 8:2, and pressing the mixture to obtain the alloy with the outer diameter ofThe coaxial sample of the iron-based amorphous nanocrystalline wave-absorbing material is prepared, and the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
As can be seen from FIG. 1, the water vapor combined atomization method adopted by the invention is used for preparing the iron-based amorphous alloy powder with the advantages of fine granularity, good sphericity, high tap density and good powder dispersibility. As can be seen from fig. 2, the iron-based amorphous powder after mechanical ball milling is deformed into a flake shape with a decrease in thickness and an increase in planar size, most of the particles are pressed into a flake having a diameter d50:13-18 μm and a thickness of 1 μm, and the aspect ratio of the iron-based amorphous powder after ball milling is significantly increased compared to the original powder of fig. 1, which has a significant effect of suppressing eddy current loss in a high-frequency electromagnetic field and improving magnetization, and greatly improving permeability and microwave absorption capacity. As can be seen from fig. 3, before heat treatment, the atomized FeSiBCrCuNbMoWC powder has a diffuse scattering peak with a lower peak intensity, the alloy has a more complete amorphous structure, and no crystalline phase is precipitated. After the amorphous powder is subjected to heat treatment at 530 ℃ for 2 hours, sharp alpha-Fe (Si) diffraction peaks appear at positions of 45.40 DEG and 83.10 DEG in an XRD diffraction spectrum, no distinguishable diffraction peaks appear at other positions, and the powder with the granularity is indicated to have weak crystallization, and the alpha-Fe (Si) nanocrystalline grain size is calculated to be about 15nm through a Shewlett-packard equation, namely the microstructure of the iron-based amorphous nanocrystalline alloy is composed of an amorphous phase matrix and alpha-Fe (Si) nanocrystalline phases distributed on the amorphous phase matrix. The influence caused by internal stress can be reduced through proper temperature heat treatment, mu is effectively improved, the epsilon value is properly reduced, impedance matching is facilitated, an amorphous/nanocrystalline composite structure is maintained, and the electromagnetic wave absorption performance can be improved through the biphase coupling effect. As can be seen from the wave-absorbing performance simulation diagram of FIG. 3, the iron-based amorphous nanocrystalline wave-absorbing material prepared by the invention has excellent broadband wave-absorbing performance, and when the thickness d=1.0 mm, RLmin can reach-15.14 dB at 8.05GHz, can cover the whole x-wave band (8-12 GHz), and has excellent high-frequency wave-absorbing performance.
Embodiment two:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the embodiment comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.0% Si,3.15% B,6.5% Cr,1.5% Cu,5.8% Nb,0.7% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 90 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 15 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 4.0mm, the atomizing pressure is 120MPa, and the atomizing water flow is 180L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 80 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m;
step three: preparing iron-based amorphous nanocrystalline wave absorbing powder: drying the iron-based amorphous powder obtained in the second step at 120 ℃ for 2.5 hours, heating to 530 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, and finally completing the transformation from amorphous state to amorphous/nanocrystalline composite double-phase structure, and then performing furnace cooling or air cooling to obtain the iron-based amorphous nanocrystalline alloy;
step four: fully mixing the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent fused thermoplastic elastomer polymer material according to the ratio of 8:2, and pressing the mixture to obtain the alloy with the outer diameter ofThe coaxial sample of the iron-based amorphous nanocrystalline wave-absorbing material is prepared, and the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
Embodiment III:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the embodiment comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.0% Si,3.15% B,6.5% Cr,1.5% Cu,5.8% Nb,0.7% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 90 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 15 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 4.0mm, the atomizing pressure is 120MPa, and the atomizing water flow is 180L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 120 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m;
step three: preparing iron-based amorphous nanocrystalline wave absorbing powder: drying the iron-based amorphous powder obtained in the second step at 120 ℃ for 2.5 hours, heating to 530 ℃ under the protection of nitrogen atmosphere, preserving heat for 3 hours, and finally completing the transformation from amorphous state to amorphous/nanocrystalline composite double-phase structure, and then performing furnace cooling or air cooling to obtain the iron-based amorphous nanocrystalline alloy;
step four: fully mixing the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent fused thermoplastic elastomer polymer material according to the ratio of 8:2, and pressing the mixture to obtain the alloy with the outer diameter ofThe coaxial sample of the iron-based amorphous nanocrystalline wave-absorbing material is prepared, and the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
Embodiment four:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the embodiment comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 70 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 10 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, and molten steel is inThe size of the drain hole at the bottom of the tundish is 4.0mm, the atomization pressure is 110MPa, and the atomization water flow is 160L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 60 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein D10 is 5-8 mu m or D50 is 13-18 mu m or D90 is 30-35 mu m;
step three: preparing iron-based amorphous nanocrystalline wave absorbing powder: drying the iron-based amorphous powder obtained in the second step at 120 ℃ for 2.5 hours, heating to 520 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, and finally completing the transformation from amorphous state to amorphous/nanocrystalline composite biphase structure, and then carrying out furnace cooling or air cooling to obtain the iron-based amorphous nanocrystalline alloy with the alpha-Fe (Si) nanocrystalline grain size of about 9 nm;
step four: fully mixing the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent fused thermoplastic elastomer polymer material according to the ratio of 8:2, and pressing the mixture to obtain the alloy with the outer diameter ofThe coaxial sample of the iron-based amorphous nanocrystalline wave-absorbing material is prepared, and the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
Fifth embodiment:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the embodiment comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 70 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 10 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 4.0mm, the atomizing pressure is 110MPa, and the atomizing water flow is 160L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 60 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein D10 is 5-8 mu m or D50 is 13-18 mu m or D90 is 30-35 mu m;
step three: preparing iron-based amorphous nanocrystalline wave absorbing powder: drying the iron-based amorphous powder obtained in the second step at 120 ℃ for 2.5 hours, heating to 550 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, and finally completing the transformation from amorphous state to amorphous/nanocrystalline composite biphase structure, and then cooling in a furnace or air to obtain the iron-based amorphous nanocrystalline alloy with the alpha-Fe (Si) nanocrystalline grain size of about 17 nm;
step four: fully mixing the iron-based amorphous nanocrystalline alloy and the electromagnetic wave transparent fused thermoplastic elastomer polymer material according to the ratio of 8:2, and pressing the mixture to obtain the alloy with the outer diameter ofThe coaxial sample of the iron-based amorphous nanocrystalline wave-absorbing material is prepared, and the prepared iron-based amorphous nanocrystalline wave-absorbing material can be used for electromagnetic parameter measurement.
Comparative example one:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the comparative example comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 70 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 10 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 4.0mm, the atomizing pressure is 110MPa, and the atomizing water flow is 160L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 60 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein D10 is 5-8 mu m or D50 is 13-18 mu m or D90 is 30-35 mu m;
step three: and (3) drying the iron-based amorphous powder obtained in the step two for 2.5 hours at the temperature of 120 ℃, then heating to 430 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, and then cooling in a furnace or cooling in air, wherein the iron-based amorphous powder is found to be incomplete in transition from an amorphous state to an amorphous/nanocrystalline composite biphasic structure. That is, it is explained that when the temperature of the heat treatment of the iron-based amorphous powder is too low, the iron-based amorphous powder cannot undergo weak crystallization.
Comparative example two:
the preparation method of the iron-based amorphous nanocrystalline wave-absorbing material in the comparative example comprises the following specific steps:
step one: preparing iron-based amorphous alloy powder:
1) Intermediate frequency induction smelting: the absorbent comprises the following components in percentage by mass: 6.5% Si,3.15% B,7.5% Cr,1.5% Cu,5.8% Nb,0.5% Mo,0.3% W,0.7% C, and the balance Fe. Preparing materials according to the components of the absorbent, selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, adding alloy raw materials into a corundum crucible, controlling smelting power to be 350KW, controlling smelting time to be 70 minutes, reducing power to be 120KW when the temperature of molten steel reaches 1500 ℃, carrying out slag-making deoxidation treatment on the molten steel by adopting 0.8kg of calcium-silicon-manganese and 1kg of lime, controlling process time to be 10 minutes, and then skimming cleanly, and casting steel.
2) Water vapor combined atomization: nitrogen is adopted as process protective atmosphere, and the flow rate of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 4.0mm, the atomizing pressure is 110MPa, and the atomizing water flow is 160L/min;
3) Vacuum drying: drying the iron-based amorphous alloy powder in a vacuum drying oven at a drying temperature of 120 ℃ and a vacuum degree of less than or equal to-0.09 MPa;
4) Screening and batch mixing treatment: air flow classification controls powder granularity and distribution, and controls powder laser granularity D50:3-6 μm.
Step two: iron-based amorphous powder preparation: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill for 60 hours to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein D10 is 5-8 mu m or D50 is 13-18 mu m or D90 is 30-35 mu m;
step three: drying the iron-based amorphous powder obtained in the second step at 120 ℃ for 2.5 hours, heating to 690 ℃ under the protection of nitrogen atmosphere, preserving heat for 2 hours, and then cooling in a furnace or air;
step four: fully mixing the material prepared in the third step with the molten thermoplastic elastomer polymer material with electromagnetic wave transparency according to the ratio of 8:2, and pressing the mixture to obtain the material with the outer diameter ofIs a coaxial sample of (c).
It is found that when the temperature of the heat treatment of the fish scale-shaped iron-based amorphous powder is too high, the material prepared in the third step contains a part of deteriorated magnetic substance, and the wave absorbing performance of the material is affected.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The novel iron-based amorphous nanocrystalline wave absorbing material is characterized by comprising an iron-based amorphous nanocrystalline alloy, wherein the iron-based amorphous nanocrystalline alloy is of an amorphous/nanocrystalline composite double-phase structure, and the iron-based amorphous nanocrystalline alloy is used as an absorbent;
the absorbent comprises the following element components in percentage by mass: 6-9% Si,2.0-3.5% B,6-8% Cr,1-3% Cu,4-7% Nb,0.4-0.8% Mo,0.3-0.6% W,0.5-0.75% C,75-79.8% Fe;
the Fe-based amorphous nanocrystalline alloy is prepared from Fe-based amorphous powder with the components through drying, and heating to a temperature higher than the initial crystallization temperature T under the protection of inert gas atmosphere X1 And lower than the second crystallization temperature T X2 Wherein T is X1 ＝515℃，T X2 =675 ℃; and preserving the heat for 2 hours, and finally cooling to room temperature to prepare the heat-insulating material;
heating to 520-550 ℃ under the protection of inert gas atmosphere;
the iron-based amorphous powder is obtained by wet grinding in a high-energy ball mill, and has D10:5-8 μm or D50:13-18 μm or D90:30-35 μm, and thickness of 0.5-1.0 μm;
the alloy also comprises a thermoplastic elastomer polymer material, wherein the mass ratio of the thermoplastic elastomer polymer material to the iron-based amorphous nanocrystalline alloy is 2:8.
2. The novel iron-based amorphous nanocrystalline wave absorbing material according to claim 1, wherein the novel iron-based amorphous nanocrystalline wave absorbing material is prepared from industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron.
3. The preparation method of the novel iron-based amorphous nanocrystalline wave-absorbing material is characterized by comprising the following steps of:
step one, preparing iron-based amorphous alloy powder: selecting industrial pure iron, pure copper, pure chromium, industrial ferroboron, monocrystalline silicon, ferroniobium and pig iron as raw materials, and performing medium-frequency induction smelting, ultrahigh-pressure water vapor combined atomization, vacuum drying, screening and batch mixing treatment on the raw materials to obtain iron-based amorphous alloy powder with the grain diameter of D50 of 3-6 mu m; the iron-based amorphous alloy powder comprises the following components in percentage by mass: 6-9% Si,2.0-3.5% B,6-8% Cr,1-3% Cu,4-7% Nb,0.4-0.8% Mo,0.3-0.6% W,0.5-0.75% C,75-79.8% Fe;
preparing iron-based amorphous powder: wet milling the iron-based amorphous alloy powder obtained in the first step in a high-energy ball mill to obtain fish scale-shaped iron-based amorphous powder with the thickness of 0.5-1.0 mu m, wherein the D10 is 5-8 mu m or the D50 is 13-18 mu m or the D90 is 30-35 mu m;
preparing the iron-based amorphous nanocrystalline alloy: the iron-based amorphous powder obtained in the second step is firstly dried and then heated to 520-550 ℃ under the protection of inert gas atmosphere, and the temperature is higher than the initial crystallization temperature T X1 And lower than the second crystallization temperature T X2 Wherein T is X1 ＝515℃，T X2 =675 ℃; and preserving heat for 2 hours, and finally cooling to room temperature to obtain the iron-based amorphous nanocrystalline alloy, wherein the iron-based amorphous nanocrystalline alloy is used as an absorbent;
the method further comprises the step four of fully mixing the iron-based amorphous nanocrystalline alloy with a matrix material according to the ratio of 8:2, and then compounding to obtain the iron-based amorphous nanocrystalline wave absorbing material; in the fourth step, the matrix material is a thermoplastic elastomer polymer material;
controlling smelting power of medium-frequency induction smelting to 300-500KW, smelting duration to 60.0-80.0 min, carrying out slag-making deoxidation treatment on molten steel by adopting 0.8kg of Si-Ca-Mn and 1kg of lime when the temperature of the molten steel reaches 1500-1520 ℃ and the power is reduced to 100-150KW, and then carrying out slag-making clean casting on the molten steel for 10.0-15.0 min;
in the first step, the ultrahigh-pressure water vapor combined atomization adopts nitrogen as a process protective atmosphere, and the flow of the nitrogen is 30.0m 3 /h; the atomizing process adopts a circular seam spray disc, the size of a leakage hole at the bottom of a molten steel tundish is 3.0-4.0mm, the atomizing pressure is 90-120MPa, and the atomizing water flow is 140-190L/min;
drying the iron-based amorphous alloy powder by adopting a vacuum drying oven, wherein the drying temperature is 130-190 ℃, and the vacuum degree is less than or equal to-0.09 MPa;
drying the iron-based amorphous alloy powder by adopting a vacuum drying oven, wherein the drying temperature is 120 ℃, and the vacuum degree is less than or equal to-0.09 MPa;
powder granularity and distribution are controlled by adopting air current classification, and powder laser granularity D50 is controlled: 3-6 μm;
in the second step, the ball milling speed of the high-energy ball mill is 200rpm-400rpm, the protective medium is ethanol, and the wet milling time is 40-60h.
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