CN108568531B - Alloyed carbonyl iron powder and preparation method thereof - Google Patents
Alloyed carbonyl iron powder and preparation method thereof Download PDFInfo
- Publication number
- CN108568531B CN108568531B CN201810381396.7A CN201810381396A CN108568531B CN 108568531 B CN108568531 B CN 108568531B CN 201810381396 A CN201810381396 A CN 201810381396A CN 108568531 B CN108568531 B CN 108568531B
- Authority
- CN
- China
- Prior art keywords
- iron
- carbonyl
- powder
- alloyed
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000000197 pyrolysis Methods 0.000 claims abstract description 26
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 21
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011358 absorbing material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910008940 W(CO)6 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- JVEVIFRPMAXOFM-UHFFFAOYSA-N [Fe].[P]=O Chemical compound [Fe].[P]=O JVEVIFRPMAXOFM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCBGPORQPUTBDJ-UHFFFAOYSA-N carbon monoxide;tungsten Chemical compound O=C=[W] KCBGPORQPUTBDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
- B22F9/305—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis of metal carbonyls
-
- B22F1/0003—
-
- 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
Abstract
The invention provides alloyed carbonyl iron powder and a preparation method thereof, mixed raw material powder containing an iron source and a non-iron metal source is mixed with carbon monoxide to carry out high-pressure gas phase reaction to obtain a mixture of carbonyl compounds; then carrying out low-pressure pyrolysis on the obtained carbonyl compound to obtain a mixture of carbonyl iron powder and carbon-based non-iron metal powder; and then annealing the obtained carbonyl metal powder mixture to obtain the alloyed carbonyl iron powder. The alloyed carbonyl iron powder prepared by the invention has excellent electromagnetic property and wave-absorbing property.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to alloyed carbonyl iron powder and a preparation method thereof.
Background
In recent years, the use frequency of electromagnetic wave components in the communication field is increased year by year, the electromagnetic wave pollution problem seriously affects the lives of military and civilian, and the electromagnetic wave components are further important for the research of electromagnetic protection. At present, the use of wave-absorbing materials has become the main method for eliminating the problem of electromagnetic wave pollution.
The commonly used wave-absorbing material is carbonyl iron powder, the carbonyl iron powder is elementary iron obtained by reducing carbonyl iron obtained by carbonyl combination, electromagnetic waves are attenuated mainly by means of magnetic loss characteristics, and the wave-absorbing material has the advantages of high saturation magnetization and high magnetic conductivity, but the carbonyl iron powder has the defects of high activity, easiness in agglomeration, easiness in polarization, high complex dielectric constant, high impedance matching difficulty in designing the wave-absorbing material and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide an alloyed carbonyl iron powder and a preparation method thereof, which can obtain an alloyed carbonyl iron powder with excellent electromagnetic properties and wave absorption properties.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of alloyed carbonyl iron powder, which comprises the following steps:
(1) providing a mixed raw material powder comprising an iron source and a non-iron metal source; the molar ratio of iron in the iron source to non-ferrous metal in the non-ferrous metal source is 1 (0.001-0.5);
(2) mixing the mixed raw material powder with carbon monoxide, and carrying out high-pressure gas phase reaction to obtain a mixture of carbonyl compounds; the pressure of the high-pressure gas-phase reaction is 20-40 MPa;
(3) performing low-pressure pyrolysis on the mixture of the carbonyl compounds obtained in the step (2) to obtain mixed metal powder; the pressure of the low-pressure pyrolysis reaction is 0.01-0.5 MPa;
(4) and (4) annealing the mixed metal powder obtained in the step (3) to obtain the alloyed carbonyl iron powder.
Preferably, the mixed raw material powder further comprises a dispersing agent and a grinding aid, and the preparation method of the mixed raw material powder comprises the following steps: carrying out wet ball milling treatment and vacuum drying treatment on the mixed slurry containing an iron source, a non-iron metal source, a dispersing agent and a grinding aid in sequence to obtain mixed raw material powder;
the wet ball milling treatment is carried out in an inert gas atmosphere;
the temperature of the vacuum drying is 80-120 ℃, and the time of the vacuum drying is 10-20 h.
Preferably, the mass ratio of the total mass of the iron source and the non-iron metal source in the mixed slurry to the grinding balls for ball milling is (30-50): 1.
preferably, the dispersant comprises one or more of calcium stearate, polyethylene glycol, cetyltrimethylammonium bromide and sodium silicate;
the mass of the dispersing agent is 0.1-10% of the total mass of the iron source and the nonferrous metal source.
Preferably, the iron source comprises sponge iron or iron oxide scale.
Preferably, the non-ferrous metal source comprises one or more of the corresponding elements of W, V, Cr, Co, Mo, Mn, Nb, Zr, and Hf, and compounds thereof.
Preferably, the temperature of the high-pressure gas phase reaction in the step (2) is 100-300 ℃, and the time of the high-pressure gas phase reaction is 100-300 h.
Preferably, the temperature of the low-pressure pyrolysis reaction in the step (3) is 200-400 ℃, and the time of the low-pressure pyrolysis reaction is 5-30 h.
Preferably, the temperature of the annealing treatment in the step (4) is 700-900 ℃, and the time of the annealing treatment is 2-10 h.
The invention also provides the alloyed carbonyl iron powder obtained by the preparation method of the technical scheme, and the chemical composition of the alloyed carbonyl iron powder is FeMxWherein x is 0.001-0.5; and M is a non-ferrous metal element.
The invention provides a preparation method of alloyed carbonyl iron powder, which comprises the following steps: mixing mixed raw material powder containing an iron source and a non-iron metal source with carbon monoxide, and carrying out high-pressure gas phase reaction to obtain a mixture of carbonyl compounds; then carrying out low-pressure pyrolysis on the obtained carbonyl compound to obtain mixed metal powder; and then annealing the obtained mixed metal powder to obtain the alloyed carbonyl iron powder. According to the invention, carbonyl compound is prepared from mixed raw material powder and carbon monoxide by a high-pressure gas phase method, and then the carbonyl compound is subjected to low-pressure pyrolysis and annealing heat treatment to obtain the final alloyed carbonyl iron powder. According to the invention, the alloyed carbonyl iron powder is obtained by carrying out a series of processes of high-pressure gas-phase synthesis, low-pressure decomposition and heat treatment on an iron source and a non-iron metal source, so that the problems of high dielectric constant and poor wave-absorbing performance of the carbonyl iron powder are solved. The results of the embodiment show that the alloyed carbonyl iron powder prepared by the method has excellent electromagnetic property and wave-absorbing property.
Drawings
FIG. 1 is a flow chart of the preparation of alloyed carbonyl iron powder provided by the invention;
FIG. 2 is an XRD pattern of alloyed carbonyl iron powder provided by the present invention;
FIG. 3 is a graph of real part of dielectric constant of alloyed carbonyl iron powder provided by the present invention;
FIG. 4 is a diagram of imaginary part of dielectric constant of alloyed carbonyl iron powder provided by the present invention;
FIG. 5 is a graph of real part of electromagnetic constant of alloyed carbonyl iron powder provided by the present invention;
fig. 6 is an imaginary part diagram of the electromagnetic constant of the alloyed carbonyl iron powder provided by the invention.
Detailed Description
The invention provides a preparation method of alloyed carbonyl iron powder, which comprises the following steps:
(1) providing a mixed raw material powder comprising an iron source and a non-iron metal source; the molar ratio of iron in the iron source to non-ferrous metal in the non-ferrous metal source is 1: (0.001 to 0.5);
(2) mixing the mixed raw material powder with carbon monoxide, and carrying out high-pressure gas phase reaction to obtain a mixture of carbonyl compounds; the pressure of the high-pressure gas-phase reaction is 20-40 MPa;
(3) performing low-pressure pyrolysis on the mixture of the carbonyl compounds obtained in the step (2) to obtain mixed metal powder; the pressure of the low-pressure pyrolysis reaction is 0.01-0.5 MPa;
(4) and (4) annealing the mixed metal powder obtained in the step (3) to obtain the alloyed carbonyl iron powder.
In the present invention, the non-ferrous metal source preferably includes one or more of the corresponding elements of W, V, Cr, Co, Mo, Mn, Nb, Zr, and Hf and compounds thereof; the present invention does not require a particular source of the non-ferrous metal source and may employ commercially available sources well known to those skilled in the art. In the present invention, the iron source preferably includes sponge iron or iron phosphorus oxide.
In the present invention, the particle size of the mixed raw material powder is preferably 0.1 to 10um, and more preferably 1 to 5 um. In the present invention, the molar ratio of iron to non-iron metal in the mixed raw material powder is 1: (0.001 to 0.5), preferably 1: (0.05 to 0.2), more preferably 1: (0.1-0.15).
In the present invention, the mixed raw material powder preferably further includes a dispersant and a grinding aid, and the method for producing the mixed raw material powder includes: and (3) carrying out wet ball milling treatment and vacuum drying treatment on the mixed slurry containing the iron source, the non-iron metal source, the dispersing agent and the grinding aid in sequence to obtain mixed raw material powder.
In the invention, the mass ratio of the total mass of the iron source and the non-iron metal source in the mixed slurry to the grinding balls for ball milling is preferably (30-50): 1, more preferably (35-45): 1, more preferably (40 to 42): 1; the grinding balls are preferably ZrO2The grinding balls preferably have a particle size of 1-10 mm.
In the present invention, the dispersant preferably includes one or more of calcium stearate, polyethylene glycol, cetyltrimethylammonium bromide, and sodium silicate. When a plurality of dispersants are selected, different kinds of dispersants are preferably added in equal parts by mass in the present invention. The source of the dispersant is not particularly critical to the present invention and may be any source known to those skilled in the art. In the present invention, the mass of the dispersant is preferably 0.1 to 10%, more preferably 1 to 8%, and still more preferably 2 to 5% of the total mass of the iron source and the nonferrous metal source.
In the invention, the grinding aid is preferably one or more of absolute ethyl alcohol, isopropanol, cyclohexane, ethylene glycol and triethanolamine; the mass of the grinding aid is preferably 200-500% of the total mass of the mixed raw material powder, and more preferably 300-400%.
In the invention, the rotation speed of the wet ball milling is preferably 500-800 rpm, more preferably 550-750 rpm, and more preferably 600-700 rpm; the wet ball milling time is preferably 5-20 h, more preferably 8-15 h, and even more preferably 10-12 h.
In the invention, the wet ball milling treatment is preferably carried out in an inert gas atmosphere, so that the introduction of impurities is avoided; the inert gas atmosphere is not particularly required in the present invention, and an inert gas atmosphere known to those skilled in the art may be used. The invention adopts wet ball milling to ensure that the particle sizes of various raw materials are uniformly distributed, thereby facilitating the full subsequent reaction and avoiding the residual raw materials and the formation of impurities caused by incomplete local reaction. In the present invention, the ball milling treatment is preferably performed in a ball mill.
After the wet ball milling, the invention preferably performs vacuum drying treatment on the ball milling slurry to obtain mixed raw material powder containing an iron source and a non-iron metal source. In the invention, the temperature of the vacuum drying is preferably 80-120 ℃, more preferably 85-110 ℃, and more preferably 90-100 ℃; the vacuum drying time is preferably 10-20 h, more preferably 12-18 h, and even more preferably 15-16 h. In the present invention, the degree of vacuum in the vacuum drying treatment is preferably 0.01 to 0.1 MPa.
After the mixed raw material powder is obtained, the mixed raw material powder is mixed with carbon monoxide to carry out high-pressure gas phase reaction to obtain the carbonyl compound. In the present invention, the mixing of the mixed raw material powder and carbon monoxide is preferably performed by placing the mixed raw material powder in a reaction vessel and then introducing carbon monoxide into the reaction vessel.
In the present invention, the pressure of the high-pressure gas phase reaction is preferably 20 to 40MPa, more preferably 25 to 35MPa, and still more preferably 30 to 32 MPa. In the invention, the temperature of the high-pressure gas phase reaction is preferably 100-300 ℃, more preferably 120-250 ℃, more preferably 150-220 ℃, and most preferably 200 ℃. In the invention, the time of the high-pressure gas phase reaction is preferably 100-300 h, more preferably 120-280 h, and even more preferably 150-200 h. In the high-pressure gas phase reaction process, the mixed raw material powder reacts with carbon monoxide to obtain a carbonyl compound Fe (CO)5、M(CO)zAnd mixtures thereof; m is a non-metal element; further preferably comprises one or more of W, V, Cr, Mo, Mn, Nb, Zr and Hf; when the preparation method contains a plurality of non-metallic elements, the invention has no special requirements on the quantity relationship of substances among different non-metallic elements, and the dosage of different non-metallic sources in the preparation method is consistent with that in the technical scheme. In the present invention, z in the carbonyl compound is determined according to the chemical valence of different nonmetallic elements.
After the high-pressure gas phase reaction, the obtained carbonyl compound is subjected to low-pressure pyrolysis to obtain mixed metal powder. In the present invention, the mixed metal powder preferably includes carbonyl iron powder and carbon-based non-iron metal powder.
In the present invention, the pressure of the low-pressure pyrolysis reaction is preferably 0.01 to 0.5MPa, more preferably 0.05 to 0.3MPa, and still more preferably 0.1 to 0.2 MPa. In the invention, the temperature of the low-pressure pyrolysis reaction is preferably 200-400 ℃, more preferably 220-350 ℃, and even more preferably 250-300 ℃. In the invention, the time of the low-pressure pyrolysis reaction is preferably 5-30 h, more preferably 8-25 h, and even more preferably 10-20 h. In the low-pressure pyrolysis reaction process, carbonyl compound Fe (CO)5、M(CO)zPyrolyzing to obtain carbonyl iron powder and carbon-based non-ironA metal powder mixture. In the present invention, the low-pressure pyrolysis reaction is preferably performed in a pyrolysis furnace.
After the low-pressure pyrolysis reaction, the obtained mixed metal powder is subjected to annealing treatment to obtain the alloyed carbonyl iron powder. In the invention, the annealing temperature is preferably 700-900 ℃, more preferably 720-880 ℃, more preferably 750-850 ℃ and most preferably 780-800 ℃. In the invention, the time of the annealing treatment is preferably 2 to 10 hours, more preferably 3 to 8 hours, and even more preferably 5 to 6 hours. The invention obtains alloyed carbonyl iron powder through annealing treatment; during the annealing treatment, carbonyl iron powder and carbonyl non-iron metal powder are partially alloyed to form FeMxThe x is 0.001-0.5, preferably 1: (0.05 to 0.2), more preferably 1: (0.1-0.15), namely the molar ratio of iron in the iron source to non-ferrous metal in the non-ferrous metal source in the preparation process of the technical scheme is consistent; m is a non-ferrous metal element; the carbonyl non-iron metal powder refers to carbonyl non-iron metal compound M (CO)zAnd (4) obtaining the elemental non-ferrous metal after pyrolysis.
The invention also provides alloyed carbonyl powder obtained by the preparation method of the technical scheme, and the chemical composition of the alloyed carbonyl powder is FeMxWherein x is 0.001-0.5; and M is a non-ferrous metal element. In the present invention, the non-ferrous metal element corresponds to the non-ferrous metal source in the preparation method according to the above technical scheme, and is not described herein again. In the present invention, the alloyed carbonyl powder comprises carbonyl iron powder and an alloyed compound.
Compared with the conventional carbonyl iron powder, the alloyed carbonyl iron powder reduces the dielectric constant and improves the magnetic conductivity, and has better wave-absorbing performance.
The alloyed carbonyl iron powder and the preparation method thereof according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Alloyed carbonyl iron powder was prepared according to the procedure shown in figure 1: sponge iron blocks and tungsten blocks with the molar ratio of 1:0.01 are mixed with each other in argon atmosphereSodium silicate dispersant, anhydrous ethanol and ZrO as grinding aid2The milling balls were wet ball milled for 5h in a ball mill at 800rpm to obtain a mixed raw material powder having a particle size of 10 μm. Wherein the dispersant is 10mm ZrO accounting for 0.1 percent of the total mass of the sponge iron block and the tungsten block2The ratio of the mass of the grinding ball to the total mass of the sponge iron block and the tungsten block is 30: 1.
And after ball milling, carrying out vacuum drying on the ball-milled slurry at 120 ℃ for 10h to obtain mixed raw material powder. Putting the mixed raw material powder into a high-temperature high-pressure reaction kettle, introducing carbon monoxide, and carrying out high-pressure gas phase reaction on the mixed raw material powder and the carbon monoxide to obtain a carbonyl compound Fe (CO)5、W(CO)6(ii) a Wherein the temperature in the reaction kettle is 100 ℃, the pressure in the kettle is 40Mpa, and the reaction time is 300 h.
Reacting a carbonyl compound Fe (CO)5、W(CO)6Performing low-pressure pyrolysis in a pyrolysis furnace with the pressure of 0.1Mpa and the temperature of 400 ℃ for 30h to obtain carbonyl iron powder and carbonyl tungsten powder, and then performing annealing heat treatment on the carbonyl metal powder at 900 ℃ for 10h to obtain alloyed carbonyl iron powder FeW0.01。
Comparative example 1
The preparation method of the conventional carbonyl iron powder comprises the following steps: the sponge iron block is mixed with dispersant sodium silicate, grinding aid anhydrous ethanol and ZrO in argon atmosphere2And carrying out wet ball milling on the grinding balls in a ball mill at 800rpm for 5h to obtain raw material iron powder with the particle size of 10 microns. Wherein the dispersant is 10mm ZrO accounting for 0.1 percent of the total mass of the sponge iron block2The ratio of the mass of the grinding ball to the total mass of the sponge iron block is 30: 1.
And (4) after ball milling, carrying out vacuum drying on the ball-milled slurry at 120 ℃ for 10h to obtain the raw material iron powder. Putting raw material iron powder into a high-temperature high-pressure reaction kettle, introducing carbon monoxide, mixing the raw material iron powder with the carbon monoxide to carry out high-pressure gas phase reaction to obtain a carbonyl compound Fe (CO)5(ii) a Wherein the temperature in the reaction kettle is 100 ℃, the pressure in the kettle is 40Mpa, and the reaction time is 300 h.
Reacting a carbonyl compound Fe (CO)5And carrying out low-pressure pyrolysis in a pyrolysis furnace with the pressure of 0.1Mpa and the temperature of 400 ℃ for 30h to obtain carbonyl iron powder.
The alloyed carbonyl iron powder obtained in example 1 was compared with a comparative conventional carbonyl iron powder.
XRD analysis was performed on the alloyed carbonyl iron powder obtained in example 1 and the carbonyl iron powder obtained in comparative example 1, and the results of the tests are shown in fig. 2. As is clear from fig. 2, the alloyed carbonyl iron powder obtained in example 1 exhibited characteristic diffraction peaks of α -Fe phase at 2 θ of 44.6 °, 65.0 ° and 82.3 °, and the diffraction peak positions were not significantly changed, and the alloying did not damage the internal structure of the carbonyl iron powder, but the amount of surface alloying was small, and the diffraction peak of the W compound was not exhibited.
The complex dielectric constant test of the alloyed carbonyl iron powder obtained in example 1 and the carbonyl iron powder obtained in comparative example 1 in the frequency range of 1-18GHz is carried out, and the results are shown in FIG. 3 and FIG. 4; as can be seen from fig. 3 and 4, the real part of the dielectric constant of the surface alloyed carbonyl iron powder obtained in example 1 tended to decrease with increasing frequency due to the dispersion phenomenon in the frequency range of 1 to 18GHz, and the decrease tendency was steep. Compared with comparative example 1, the real part and the imaginary part of the dielectric constant of the surface alloyed carbonyl iron powder obtained in example 1 are both greatly reduced, and the surface alloying reduces the dielectric polarization degree of the carbonyl iron, so that the dielectric constant is reduced.
The complex permeability constant test of the alloyed carbonyl iron powder obtained in example 1 and the carbonyl iron powder obtained in comparative example 1 in the frequency range of 1-18GHz is carried out, and the results are shown in FIG. 5 and FIG. 6; as is clear from fig. 5 and 6, the alloyed carbonyl iron powder obtained in example 1 had a tendency that the real part of the permeability constant decreased with an increase in frequency and the decreasing tendency became gentler as the frequency was higher due to the dispersion phenomenon in the frequency range of 1 to 18 GHz.
The imaginary part of the magnetic permeability shows an ascending trend at 1-6GHz and shows a descending trend at 6-18 GHz. A more pronounced magnetic loss peak occurs at the 6GHz frequency point. The rate of decrease in the real part of high-frequency permeability of the example was significantly slowed down compared to comparative example 1. The reduction of the dielectric constant and the increase of the magnetic permeability of the embodiment are both beneficial to enhancing the microwave absorption and can improve the microwave absorption performance.
The embodiment shows that the alloyed carbonyl iron powder prepared by the invention has excellent electromagnetic property and wave-absorbing property.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of alloyed carbonyl iron powder comprises the following steps:
(1) providing a mixed feedstock powder comprising an iron source, a non-iron metal source, a dispersant, and a grinding aid; the molar ratio of iron in the iron source to non-ferrous metal in the non-ferrous metal source is 1 (0.001-0.5); the iron source comprises sponge iron or ferric oxide scale;
the preparation method of the mixed raw material powder comprises the following steps: carrying out wet ball milling treatment and vacuum drying treatment on the mixed slurry containing an iron source, a non-iron metal source, a dispersing agent and a grinding aid in sequence to obtain mixed raw material powder; the wet ball milling treatment is carried out in an inert gas atmosphere; the temperature of the vacuum drying is 80-120 ℃, and the time of the vacuum drying is 10-20 h;
(2) mixing the mixed raw material powder with carbon monoxide, and carrying out high-pressure gas phase reaction to obtain a mixture of carbonyl compounds; the pressure of the high-pressure gas-phase reaction is 20-40 MPa; the temperature of the high-pressure gas-phase reaction is 100-300 ℃, and the time of the high-pressure gas-phase reaction is 100-300 h;
(3) performing low-pressure pyrolysis on the mixture of the carbonyl compounds obtained in the step (2) to obtain mixed metal powder; the pressure of the low-pressure pyrolysis reaction is 0.01-0.5 MPa; the temperature of the low-pressure pyrolysis reaction is 200-400 ℃, and the time of the low-pressure pyrolysis reaction is 5-30 hours;
(4) annealing the mixed metal powder obtained in the step (3) to obtain alloyed carbonyl iron powder; the temperature of the annealing treatment is 700-900 ℃, and the time of the annealing treatment is 2-10 h.
2. The preparation method according to claim 1, wherein the mass ratio of the total mass of the iron source and the non-iron metal source to the grinding balls for ball milling in the mixed slurry is (30-50): 1.
3. the method of claim 1, wherein the dispersant comprises one or more of calcium stearate, polyethylene glycol, cetyltrimethylammonium bromide, and sodium silicate;
the mass of the dispersing agent is 0.1-10% of the total mass of the iron source and the nonferrous metal source.
4. The method according to any one of claims 1 to 3, wherein the non-ferrous metal source comprises one or more of corresponding elements of W, V, Cr, Co, Mo, Mn, Nb, Zr, and Hf, and compounds thereof.
5. The alloyed carbonyl iron powder obtained by the preparation method of any one of claims 1 to 4, wherein the chemical composition is FeMx, and x is 0.001 to 0.5; and M is a non-ferrous metal element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810381396.7A CN108568531B (en) | 2018-04-25 | 2018-04-25 | Alloyed carbonyl iron powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810381396.7A CN108568531B (en) | 2018-04-25 | 2018-04-25 | Alloyed carbonyl iron powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108568531A CN108568531A (en) | 2018-09-25 |
| CN108568531B true CN108568531B (en) | 2021-05-11 |
Family
ID=63575314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810381396.7A Active CN108568531B (en) | 2018-04-25 | 2018-04-25 | Alloyed carbonyl iron powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108568531B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110722153B (en) * | 2019-11-25 | 2021-07-27 | 西安航空学院 | Antioxidant absorbent and preparation method thereof |
| CN111926365A (en) * | 2020-07-13 | 2020-11-13 | 赣南师范大学 | Magnesium alloy micro-arc oxidation efficient electromagnetic shielding coating and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10358074A1 (en) * | 2003-12-10 | 2005-07-21 | Basf Ag | Process for the preparation of iron pentacarbonyl |
| CN101696038B (en) * | 2009-10-26 | 2011-08-10 | 江西悦安超细金属有限公司 | Method for preparing carbonyl iron powder in high-pressure circulating way |
| CN104478005A (en) * | 2014-12-07 | 2015-04-01 | 金川集团股份有限公司 | Method for preparing carbonyl iron |
| CN105965033B (en) * | 2016-05-23 | 2018-02-06 | 江油核宝纳米材料有限公司 | The preparation method of micron order carbonyl iron, nickel alloy powder |
| CN105948138A (en) * | 2016-06-22 | 2016-09-21 | 金川集团股份有限公司 | Preparation method of carbonyl ferronickel alloy powder |
| CN107043134B (en) * | 2017-01-10 | 2018-09-14 | 南京邮电大学 | Preparation method based on Bluetooth communication frequency range application flaky carbonyl iron powder absorbing material |
| CN106946295B (en) * | 2017-02-24 | 2018-11-02 | 华南理工大学 | A kind of method that plasmaassisted ball milling prepares flaky carbonyl iron powder |
-
2018
- 2018-04-25 CN CN201810381396.7A patent/CN108568531B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108568531A (en) | 2018-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108154984B (en) | Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof | |
| CN109762519B (en) | Preparation method of high-entropy alloy/oxide composite nano wave-absorbing material | |
| CN108568531B (en) | Alloyed carbonyl iron powder and preparation method thereof | |
| CN103626181A (en) | Method for preparing uniform and ultrafine tungsten carbide | |
| Wang et al. | Electromagnetic and wave absorbing properties of Fe-doped polymer-derived SiCN ceramics | |
| CN105702410A (en) | Method for preparing soft magnetic powder core | |
| CN108610037B (en) | Manganese-zinc high-permeability material with wide temperature range and high Curie temperature superposition and preparation method thereof | |
| CN113896543A (en) | Wave-absorbing silicon-carbon-nitrogen ceramic with layered structure and preparation method thereof | |
| CN114845538A (en) | Magnetic metal @ carbon composite wave-absorbing material derived from layered double-magnetic metal hydroxide and preparation method thereof | |
| CN113380483B (en) | Composite soft magnetic material and preparation method thereof | |
| CN105016395A (en) | Nano ferrite material, and preparation method thereof | |
| CN101955184A (en) | Method for preparing novel nanoscale chrome carbide powder | |
| Xia et al. | Hydrothermal hexagonal SrFe 12 O 19 ferrite powders: Phase composition, microstructure and acid washing | |
| Liu et al. | In situ construction of complex spinel ferrimagnet in multi-elemental alloy for modulating natural resonance and highly efficient electromagnetic absorption | |
| CN114334423A (en) | Iron-based nitride soft magnetic material and preparation method thereof | |
| CN112194482B (en) | Ultralow-loss wide-temperature-power MnZn ferrite, preparation method and application thereof in 5G communication field | |
| CN111613901B (en) | Graphene/metal oxide/metal ternary nano composite magnetic material and preparation method thereof | |
| KR101429530B1 (en) | Flake powder for electromagnetic wave absorber and method for manufacturing the same | |
| CN109704749B (en) | Ultrahigh frequency low-loss soft magnetic ferrite material and preparation method and application of magnetic core | |
| CN112573925B (en) | High-performance electromagnetic shielding NdB 6 /SiO 2 Complex phase ceramic material and preparation method thereof | |
| CN110517723B (en) | Preparation method of high-permeability GHz-band absorbing material | |
| CN113708085B (en) | Preparation method of nano porous carbon coated magnetic nanoparticle compound | |
| CN112745694B (en) | Petroleum asphalt/ferroferric oxide composite wave absorbing agent, preparation method thereof and wave absorbing material | |
| CN114684802B (en) | Magnetic iron-cobalt-nickel alloy/carbon series composite wave-absorbing material and preparation method and application thereof | |
| JP7209761B2 (en) | NEAR FIELD NOISE SUPPRESSION SHEET AND MANUFACTURING METHOD THEREOF |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |