CN116689748A - Modified carbonyl iron powder and preparation method and application thereof - Google Patents
Modified carbonyl iron powder and preparation method and application thereof Download PDFInfo
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- CN116689748A CN116689748A CN202310715049.4A CN202310715049A CN116689748A CN 116689748 A CN116689748 A CN 116689748A CN 202310715049 A CN202310715049 A CN 202310715049A CN 116689748 A CN116689748 A CN 116689748A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007747 plating Methods 0.000 claims abstract description 92
- 238000010438 heat treatment Methods 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 35
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000011358 absorbing material Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims description 22
- 238000005530 etching Methods 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 17
- 230000007704 transition Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 7
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 239000002923 metal particle Substances 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 60
- 239000008139 complexing agent Substances 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000007772 electroless plating Methods 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000872 buffer Substances 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 238000003012 network analysis Methods 0.000 description 4
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 241000080590 Niso Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical group [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 3
- 239000001433 sodium tartrate Substances 0.000 description 3
- 229960002167 sodium tartrate Drugs 0.000 description 3
- 235000011004 sodium tartrates Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HDEPFLVKWKPGFZ-UHFFFAOYSA-N Cl(=O)(=O)O.[Pt] Chemical compound Cl(=O)(=O)O.[Pt] HDEPFLVKWKPGFZ-UHFFFAOYSA-N 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/30—Energy from the sea, e.g. using wave energy or salinity gradient
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention provides modified carbonyl iron powder and a preparation method thereof, and belongs to the technical field of electromagnetic wave absorbing materials. The surface of the carbonyl iron powder is activated, so that the surface of the iron powder can be roughened, appointed metal particles can be reduced on the surface of the iron powder during chemical plating, and the reduction reaction is accelerated during chemical plating; according to the invention, the metal coating is formed on the surface of the iron powder through chemical plating, so that the electromagnetic performance of carbonyl iron powder can be improved; according to the invention, the surface metal coating and the carbonyl iron powder at the bottom layer are mutually diffused through vacuum heat treatment to form a layer of alloy diffusion layer, so that the magnetic continuity of the surface of the iron powder is ensured while the performance of the iron powder is improved; the invention forms a compact oxide film on the surface of the alloyed carbonyl iron powder by controlling oxidation, thereby greatly improving the corrosion resistance of the carbonyl iron powder.
Description
Technical Field
The invention relates to the technical field of electromagnetic wave absorbing materials, in particular to modified carbonyl iron powder and a preparation method and application thereof.
Background
Wave absorbing materials refer to materials that absorb or substantially attenuate electromagnetic wave energy received at their surfaces, thereby reducing electromagnetic wave interference. The wave absorbing material is mainly used for attenuating and losing electromagnetic waves by using an absorbent, wherein the most commonly used absorbent is carbonyl iron powder. However, with the improvement of modern military countermeasure technologies, the use of carbonyl iron powder is severely limited by the disadvantages of excessively high conductivity, excessively high complex dielectric constant, poor impedance matching characteristics, and poor oxidation resistance and acid-base resistance of the carbonyl iron powder.
At present, the modification of carbonyl iron powder by researchers mainly comprises the steps of wrapping carbonyl iron powder to form a core-shell structure, and the common method comprises the following steps: 1) The physical method realizes the core-shell structure through the surface adsorption, and generally comprises an atomic layer deposition method and a mechanical ball milling method; 2) The chemical method is to obtain a core-shell structure through chemical reaction of the surface additive and the particles, and mainly comprises chemical plating, vapor deposition, sol-gel, precipitation method and the like. However, for the modification method, if a single coated metal is adopted, most of the magnetic metal has weaker magnetism than carbonyl iron powder and strong conductivity, so that the serious skin effect of the carbonyl iron powder cannot be improved, the impedance matching performance is poor, the electromagnetic performance is not increased much, the surface activity of the chemically coated metal is larger, and the chemically coated metal is easy to oxidize; if the non-metal oxide is used for coating, the dielectric parameter of carbonyl iron powder can be improved, but the combination of the non-metal and the surface of the iron particles is not compact, and the non-metal oxide coating has obvious interface layer and can not improve the characteristic that the iron powder is not acid and alkali corrosion resistant.
Therefore, how to improve the dielectric property, acid and alkali corrosion resistance, impedance matching and other properties of carbonyl iron powder is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide modified carbonyl iron powder, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of modified carbonyl iron powder, which comprises the following steps:
(1) Performing surface activation on carbonyl iron powder to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder;
(3) And (3) sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder.
Preferably, the surface activation in step (1) includes: and etching carbonyl iron powder in the etching solution.
Preferably, the pH value of the etching solution is 1-3.
Preferably, the plating metal electroless plated in the step (2) includes one or more of Ni, co, cu, sn, in, ag, au, pt, rh, pd, ir, W, mo and Zn.
Preferably, the vacuum heat treatment in the step (3) includes a low-temperature heat treatment and a high-temperature heat treatment which are sequentially performed.
Preferably, the temperature of the low-temperature heat treatment is 500-650 ℃; the low-temperature heat treatment time is 2-6 h.
Preferably, the temperature of the high-temperature heat treatment is 800-950 ℃; the high-temperature heat treatment time is 4-8 hours.
Preferably, the partial pressure of oxygen in the oxidation is controlled to be 0.3% -8% in the step (3).
The invention also provides the modified carbonyl iron powder prepared by the preparation method of the technical scheme, which comprises carbonyl iron powder, a transition alloy layer and a metal plating layer coated on the surface of the transition alloy layer.
The invention also provides application of the modified carbonyl iron powder in the wave-absorbing material.
The invention provides a preparation method of modified carbonyl iron powder, which comprises the following steps: performing surface activation on carbonyl iron powder to obtain pretreated carbonyl iron powder; performing chemical plating on the pretreated carbonyl iron powder to obtain composite carbonyl iron powder; and sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder to obtain the modified carbonyl iron powder. According to the invention, the surface of the carbonyl iron powder is roughened by activating the surface of the iron powder, so that appointed metal particles can be reduced on the surface of the iron powder during electroless plating, and the surface-activated iron powder has a certain catalytic reaction effect during electroless plating, so that the reduction reaction can be accelerated; the invention forms a metal coating on the surface of the iron powder by chemical plating, and canThe electromagnetic performance of carbonyl iron powder is improved; according to the invention, the surface metal coating and the carbonyl iron powder at the bottom layer are mutually diffused through vacuum heat treatment to form a layer of alloy diffusion layer, so that the magnetic continuity of the surface of the iron powder is ensured while the performance of the iron powder is improved; the invention forms a compact oxide film on the surface of the alloyed carbonyl iron powder by controlling oxidation, thereby greatly improving the corrosion resistance of the carbonyl iron powder. The results of the examples show that the modified carbonyl iron powder prepared by the preparation method provided by the invention has a sample test R of 1.5mm L The maximum is-45 dB, and the bandwidth is 8.2-12.4 GHz; and has excellent corrosion resistance.
Detailed Description
The invention provides a preparation method of modified carbonyl iron powder, which comprises the following steps:
(1) Performing surface activation on carbonyl iron powder to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder;
(3) And (3) sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder.
The invention carries out surface activation on carbonyl iron powder to obtain pretreated carbonyl iron powder. In the invention, the surface activation can roughen the surface of the iron powder, and the metal particles can be reduced on the surface of the iron powder during the chemical plating; in addition, the etched iron powder has a certain catalytic reaction effect during electroless plating, and can accelerate the reduction reaction.
The size and source of the carbonyl iron powder are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the surface activation preferably includes: and etching carbonyl iron powder in the etching solution. In the present invention, the etching solution preferably comprises an aqueous solution composed of one or more of citric acid, hydrochloric acid, sulfuric acid, oxalic acid, malic acid, and tartaric acid; the concentration of the acid in the etching solution is preferably 0.1 to 1mol/L, more preferably 0.5 to 1mol/L. In the invention, when the etching solution is of the type, the surface activation of carbonyl iron powder is more facilitated.
In the present invention, the pH of the etching solution is preferably 1 to 3, more preferably 2 to 3; the etching time is preferably 2 to 8 minutes, more preferably 4 to 6 minutes. In the invention, when the pH value and the etching time of the etching solution are in the above ranges, the iron powder can be etched rapidly, so that the surface of the iron powder is fully activated.
In the present invention, the etching solution preferably further includes a surfactant. In the invention, when the wettability of the carbonyl iron powder with water is poor, the surfactant is added into the etching solution, so that the dispersion of the carbonyl iron powder in the water can be promoted, and the etching of the carbonyl iron powder by the etching solution can be promoted. In the present invention, the surfactant preferably includes one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and Gemini surfactant; the addition amount of the surfactant is preferably 0.1 to 0.3% by mass of the etching solution, more preferably 0.2 to 0.3%.
After the surface activation is completed, the powder obtained after the surface activation is preferably filtered and washed in sequence to obtain the pretreated carbonyl iron powder. In the invention, the filtering and washing can remove the etching solution on the surface of the pretreated carbonyl iron powder, thereby preventing the influence on the subsequent electroless plating. The method of operation of the filtration and washing is not particularly limited in the present invention, and filtration and washing methods well known to those skilled in the art may be employed. In the present invention, the washed reagent is preferably water.
After the pretreated carbonyl iron powder is obtained, the invention carries out chemical plating on the pretreated carbonyl iron powder to obtain the composite carbonyl iron powder.
In the present invention, the electroless plated metal preferably includes one or more of Ni, co, cu, sn, in, ag, au, pt, rh, pd, ir, W, mo and Zn, more preferably includes one or more of Co, ni, pt, cu, sn and Ag. In the present invention, when the plating metal is of the above type, the electromagnetic properties of carbonyl iron powder can be improved.
The plating solution for electroless plating is not particularly limited, and the metal plating layer can be formed on the surface of carbonyl iron powder by using a plating solution known to those skilled in the art. In the present invention, the electroless plating solution preferably includes a metal salt, a complexing agent, a pH adjustor, a wetting agent, a buffering agent, and a reducing agent.
In the present invention, the metal salt preferably includes one or more of Ni, co, cu, sn, in, ag, au, pt, rh, pd, ir, W, mo and Zn, more preferably includes one or more of Co, ni, pt, cu, sn and Ag. In the present invention, the cobalt salt preferably includes cobalt sulfate or cobalt sulfamate; the concentration of cobalt salt in the plating solution is preferably 30-60 g/L, more preferably 40-50 g/L; the nickel salt in the plating solution preferably comprises nickel sulfate, nickel chloride or nickel sulfamate; the concentration of nickel salt in the plating solution is preferably 30-60 g/L, more preferably 40-50 g/L; the platinum salt preferably comprises dinitrodiamine platinum or platinum chloric acid; the concentration of the platinum salt in the plating solution is preferably 5-10 g/L, more preferably 6-8 g/L; the copper salt preferably comprises copper sulfate or copper chloride; the concentration of copper salt in the plating solution is preferably 5-20 g/L, more preferably 10-15 g/L; the tin salt preferably comprises stannous chloride; the concentration of the tin salt in the plating solution is preferably 80-120 g/L, more preferably 100-110 g/L; the silver salt preferably comprises silver nitrate; the concentration of silver salt in the plating solution is preferably 10 to 20g/L, more preferably 15 to 20g/L. In the present invention, when the type and concentration of the metal salt are in the above-described ranges, a metal plating layer having a uniform thickness can be formed on the metal carbonyl surface.
In the present invention, the complexing agent preferably comprises one or more of citrate, tartrate, pyrophosphate, EDTA and malate. The dosage of the complexing agent is not particularly limited, and the complexing agent can be adjusted according to experimental requirements. In the present invention, the citrate is preferably used in an amount close to that of the metal salt; the dosage of the tartrate is preferably 1.5 to 2 times of that of the metal salt; the dosage of the pyrophosphate is preferably 1.5 to 2 times of that of the metal salt.
In the present invention, the pH adjuster is preferably aqueous ammonia. In the invention, the ammonia water is a strong complexing agent and can be complexed with metal ions, so that the deposition rate of electroless plating is more gentle. The amount of the pH adjustor is not particularly limited, and the pH adjustor can be adjusted according to the pH required by the plating solution. In the present invention, when the plating layer is cobalt, the pH adjuster is preferably added in an amount to adjust the pH of the plating solution to 6 to 8.
In the present invention, the reducing agent preferably includes sodium phosphite or aminoborane. In the invention, the introduction of a proper amount of P in the sodium phosphite series reducing agent can improve the magnetic coercivity of iron powder to a certain extent, and the aminoborane series reducing agent is green, environment-friendly and nontoxic.
In the present invention, the addition amount of the sodium phosphite is preferably 20 to 40g/L, more preferably 30 to 35g/L; the amount of the aminoborane to be added is preferably 3 to 6g/L, more preferably 4 to 5g/L. In the present invention, when the addition amount of the sodium phosphite and the aminoborane is in the above-described range, the metal ions can be sufficiently reduced to the metal simple substance.
The type and amount of the wetting agent are not particularly limited, and may be selected as needed.
The kind and amount of the buffer are not particularly limited in the present invention, and may be selected as needed. In the present invention, the buffer game includes ammonium chloride.
In the present invention, the thickness of the plating layer obtained by electroless plating is preferably 1 to 5. Mu.m, more preferably 1 to 3. Mu.m. In the present invention, when the thickness of the plating layer is in the above range, the electromagnetic properties of the modified carbonyl iron powder can be sufficiently improved. The invention adjusts the thickness of the plating layer by controlling the temperature and time of the chemical plating. In the present invention, the electroless plating temperature is preferably 40 to 80 ℃, more preferably 60±5 ℃; the electroless plating time is preferably 10 to 60 minutes, more preferably 15 to 30 minutes. In the present invention, when the temperature and time of the electroless plating are in the above ranges, the plating layer can be made to have a desired thickness that sufficiently improves the electromagnetic properties of the modified carbonyl iron powder.
After the composite carbonyl iron powder is obtained, the composite carbonyl iron powder is subjected to vacuum heat treatment and controlled oxidation in sequence to obtain the modified carbonyl iron powder.
In the present invention, the vacuum heat treatment preferably includes a low-temperature heat treatment and a high-temperature heat treatment which are sequentially performed.
The temperature of the low-temperature heat treatment in the present invention is preferably 500 to 650 ℃, more preferably 550 to 600 ℃; the time of the low-temperature heat treatment is preferably 2 to 6 hours, more preferably 4 hours. In the invention, the metal coated on the surface of the composite carbonyl iron powder is an amorphous metal phase, and the amorphous metal phase on the surface can be converted into crystals and grow through low-temperature heat treatment, so that the metal is more densely coated on the surface of the iron powder. When the temperature of the low-temperature heat treatment is in the above range, the inter-diffusion of the deposited metal and the underlying metal can be avoided, but the deposited metal can be converted into metallographic crystals and grow.
After the low-temperature heat treatment is completed, the present invention preferably heats the product of the low-temperature heat treatment directly to the temperature of the low-temperature heat treatment. In the present invention, the temperature of the high-temperature heat treatment is preferably 800 to 950 ℃, more preferably 850 to 900 ℃; the time of the high temperature heat treatment is preferably 4 to 8 hours, more preferably 6 hours. In the present invention, the low-temperature heat treatment is directly followed by the high-temperature heat treatment to allow the iron and the surface-coated metal to diffuse into each other. When the temperature of the high-temperature heat treatment is in the range, the deposited metal and the bottom iron can be mutually diffused and reacted to form a transition alloy layer, and the diffusion depth of the surface metal and the iron powder can be controlled to reach the required requirement by controlling the diffusion temperature and the diffusion time to be in the range.
In the present invention, the partial pressure of oxygen for controlling oxidation is preferably 0.3% to 8%, more preferably 0.3% to 8%, and still more preferably 6% to 8%. In the invention, when the partial pressure of oxygen for controlling oxidation is in the range, a compact oxide film can be formed on the surface of the alloyed carbonyl iron powder, so that the corrosion resistance of the carbonyl iron powder is improved; and can avoid the iron powder forming nonmagnetic Fe 2 O 3 Or FeO, preferably forming magnetic Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Spinel structures, such as NiFe, which are preferentially formed with magnetism when the surface is coated with a metal or alloyed iron powder 2 O 4 Or CoFe 2 O 4 Etc.
The method of controlling the oxidation according to the present invention is not particularly limited, and the above-described oxygen partial pressure range may be realized. In the present invention, the controlled oxidation preferably includes: paving the powder obtained by the vacuum heat treatment on a ceramic plate; then placing the ceramic plate filled with the powder into a vacuum device, mixing oxygen and argon according to a certain proportion, and slowly introducing the mixture into the vacuum device. In the present invention, the temperature of the controlled oxidation is preferably 550 to 750 ℃, more preferably 650±50 ℃; the time for controlling the oxidation is preferably 4 to 10 hours, more preferably 6 to 8 hours.
The vacuum apparatus is not particularly limited, and any apparatus capable of realizing vacuum, which is well known to those skilled in the art, may be used. In the present invention, the vacuum apparatus preferably includes a vacuum furnace or an atmosphere furnace.
The invention preferably pumps the pressure in the vacuum device to less than or equal to 10 before the oxygen and the argon are mixed according to a certain proportion and then are slowly introduced into the vacuum device -3 Pa. In the invention, the pressure in the vacuum device is pumped to be less than or equal to 10 -3 Pa can ensure that the air in the furnace is completely pumped out, and the partial pressure of oxygen and argon can be conveniently controlled subsequently.
The apparatus used for introducing the oxygen and argon into the vacuum apparatus is not particularly limited, and a gas mixing system well known to those skilled in the art may be used.
According to the invention, the surface of the carbonyl iron powder is roughened by activating the surface of the iron powder, so that appointed metal particles can be reduced on the surface of the iron powder during electroless plating, and the surface-activated iron powder has a certain catalytic reaction effect during electroless plating, so that the reduction reaction can be accelerated; according to the invention, the metal coating is formed on the surface of the iron powder through chemical plating, so that the electromagnetic performance of carbonyl iron powder can be improved; according to the invention, the surface metal coating and the carbonyl iron powder at the bottom layer are mutually diffused through vacuum heat treatment to form a layer of alloy diffusion layer, so that the magnetic continuity of the surface of the iron powder is ensured while the performance of the iron powder is improved; the invention forms a compact oxide film on the surface of the alloyed carbonyl iron powder by controlling oxidation, thereby improving the corrosion resistance of the carbonyl iron powder.
The invention also provides the modified carbonyl iron powder prepared by the preparation method of the technical scheme, which comprises carbonyl iron powder, a transition alloy layer coated on the surface of the carbonyl iron powder, a metal coating coated on the surface of the transition alloy layer and an oxide film coated on the surface of the metal coating. The transition alloy layer is arranged between the metal coating of the modified carbonyl iron powder and the carbonyl iron powder, and the metal coating tightly wraps the carbonyl iron powder, so that the metal coating and the carbonyl iron powder can be prevented from being combined untight, and the modified carbonyl iron powder has excellent dielectric property, acid-base resistance and impedance matching property.
The invention also provides application of the modified carbonyl iron powder in the wave-absorbing material.
The application method of the modified carbonyl iron powder in the wave-absorbing material is not particularly limited, and the application method well known to the person skilled in the art can be adopted.
The modified carbonyl iron powder provided by the invention has excellent dielectric property, acid-base resistance and impedance matching property, and can be further used for wave-absorbing materials.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of modified carbonyl iron powder comprises the following steps:
(1) Performing surface activation on carbonyl iron powder in 0.1mol/L hydrochloric acid dilute solution with the pH value of 1 for 3min, and washing to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder;
wherein the thickness of the plating layer of the chemical plating is 3 mu m, the temperature of the chemical plating is 65 ℃ and the time is 30min; the plating metal is Co, and the plating solution formula of the chemical plating is as follows: metal saltsIs CoSO 4 : the concentration of metal salt in the plating solution is 30g/L, and the complexing agent is sodium tartrate: the concentration of the complexing agent in the plating solution is 80g/L, and the complexing agent is sodium citrate: the concentration of the complexing agent in the plating solution is 10g/L, the buffer ammonium chloride is 20g, the pH regulator is ammonia water, the dosage of the ammonia water is 60mL, the concentration is 1mol/L, and the reducing agent is DMAB: the concentration of DMAB in the plating solution is 3g/L, and the pH value of the plating solution for electroless plating is about 8.5;
(3) Sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder;
the vacuum heat treatment comprises a low-temperature heat treatment and a high-temperature heat treatment which are sequentially carried out, wherein the temperature of the low-temperature heat treatment is 600 ℃, the time of the low-temperature heat treatment is 2 hours, the temperature of the high-temperature heat treatment is 900 ℃, and the time of the high-temperature heat treatment is 2 hours;
wherein the step of controlling oxidation is: paving the powder obtained by the vacuum heat treatment on a ceramic plate; then placing the ceramic plate with the powder into a vacuum device, and pumping the pressure in the vacuum device to be less than or equal to 10 -3 Pa, oxygen and argon are controlled to have oxygen partial pressure of 0.5% according to a certain proportion, and are slowly introduced into a vacuum device to control oxidization, wherein the temperature of the oxidization is controlled to be 680 ℃ and the time is 6 hours.
Example 2
A preparation method of modified carbonyl iron powder comprises the following steps:
(1) Performing surface activation on carbonyl iron powder in a hydrochloric acid dilute solution with the pH value of 1 for 3min, and washing to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder; wherein, the thickness of the plating layer of the chemical plating is 5 mu m, the temperature of the chemical plating is 65 ℃ and the time is 40min; the plating metal is Ni, and the plating solution formula of the chemical plating is as follows: the metal salt is NiSO 4 : the concentration of metal salt in the plating solution is 30g/L, and the complexing agent is sodium citrate: the concentration of the complexing agent in the plating solution is 30g/L, the buffer agent is 20g/L of ammonium chloride, the pH regulator is ammonia water, the dosage of the ammonia water is 10mL, the concentration is 10mol/L, and the reducing agent is DMAB: the concentration of DMAB in the plating solution is 3g/L, and the pH value of the plating solution for electroless plating is 5.5；
(3) Sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder;
the method comprises low-temperature heat treatment and high-temperature heat treatment which are sequentially carried out, wherein the temperature of the low-temperature heat treatment is 550 ℃, the time of the low-temperature heat treatment is 2 hours, the temperature of the high-temperature heat treatment is 870 ℃, and the time is 4 hours;
wherein the step of controlling oxidation is: paving the powder obtained by the vacuum heat treatment on a ceramic plate; then placing the ceramic plate with the powder into a vacuum device, and pumping the pressure in the vacuum device to be less than or equal to 10 -3 Pa, oxygen and argon are controlled to have oxygen partial pressure of 0.5% according to a certain proportion, and are slowly introduced into a vacuum device to control oxidization, wherein the temperature of the oxidization is controlled to be 680 ℃ and the time is 6 hours.
Example 3
A preparation method of modified carbonyl iron powder comprises the following steps:
(1) Performing surface activation on carbonyl iron powder in a hydrochloric acid dilute solution with the pH value of 1 for 3min, and washing to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder; wherein the thickness of the plating layer of the chemical plating is 3 mu m, the temperature of the chemical plating is 65 ℃ and the time is 30min; the plating metal is Co, and the plating solution formula of the chemical plating is as follows: the metal salt is CoSO 4 : the concentration of metal salt in the plating solution is 30g/L, and the complexing agent is sodium tartrate: the concentration of the complexing agent in the plating solution is 80g/L, and the complexing agent is sodium citrate: the concentration of the complexing agent in the plating solution is 10g/L, the buffer agent is 20g/L of ammonium chloride, the pH regulator is ammonia water, the dosage of the ammonia water is 50mL, and the reducer is sodium hypophosphite: the concentration of sodium hypophosphite in the plating solution is 30g/L, and the pH value of the plating solution for electroless plating is 7.5;
(3) Sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder;
the vacuum heat treatment comprises a low-temperature heat treatment and a high-temperature heat treatment which are sequentially carried out, wherein the temperature of the low-temperature heat treatment is 600 ℃, the time of the low-temperature heat treatment is 2 hours, the temperature of the high-temperature heat treatment is 900 ℃, and the time of the high-temperature heat treatment is 2 hours;
wherein the step of controlling oxidation is: paving the powder obtained by the vacuum heat treatment on a ceramic plate; then placing the ceramic plate with the powder into a vacuum device, and pumping the pressure in the vacuum device to be less than or equal to 10 -3 Pa, oxygen and argon are controlled to have oxygen partial pressure of 0.5% according to a certain proportion, and are slowly introduced into a vacuum device to control oxidization, wherein the temperature of the oxidization is controlled to be 700 ℃ and the time is 4 hours.
Example 4
A preparation method of modified carbonyl iron powder comprises the following steps:
(1) Performing surface activation on carbonyl iron powder in a hydrochloric acid dilute solution with the pH value of 1 for 3min, and washing to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder; wherein the thickness of the plating layer of the chemical plating is 3 mu m, the temperature of the chemical plating is 65 ℃ and the time is 30min; the plating metal is Ni, and the plating solution formula of the chemical plating is as follows: the metal salt is NiSO 4 : the concentration of metal salt in the plating solution is 30g/L, and the complexing agent is sodium citrate: the concentration of the complexing agent in the plating solution is 30g/L, the buffer agent is 20g of ammonium chloride, the pH regulator is ammonia water, the dosage of the ammonia water is 10mL, and the reducing agent is DMAB: the concentration of DMAB in the plating solution is 3g/L, and the pH value of the plating solution for electroless plating is 5.5;
(3) Sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder;
the vacuum heat treatment comprises a low-temperature heat treatment and a high-temperature heat treatment which are sequentially carried out, wherein the temperature of the low-temperature heat treatment is 600 ℃, the time of the low-temperature heat treatment is 2 hours, the temperature of the high-temperature heat treatment is 950 ℃, and the time is 2 hours;
wherein the step of controlling oxidation is: paving the powder obtained by the vacuum heat treatment on a ceramic plate; then placing the ceramic plate with the powder into a vacuum device, and pumping the pressure in the vacuum device to be less than or equal to 10 -3 Pa, controlling the partial pressure of oxygen and argon to be 0.3% according to a certain proportion, and slowing downSlowly introducing a vacuum device to control oxidation, wherein the temperature of the oxidation is 650 ℃ and the time is 10 hours.
Example 5
A preparation method of modified carbonyl iron powder comprises the following steps:
(1) Performing surface activation on carbonyl iron powder in a hydrochloric acid dilute solution with the pH value of 1 for 3min, and washing to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder; wherein, the thickness of the plating layer of the chemical plating is 5 mu m, the temperature of the chemical plating is 65 ℃ and the time is 40min; the plating metal is a Co and Ni compound, and the plating solution formula of the chemical plating is as follows: the metal salt is CoSO 4 、NiSO 4 : the concentration of metal salt in the plating solution is 30g/L and 30g/L respectively, and the complexing agent is sodium tartrate: the concentration of the complexing agent in the plating solution is 80g/L, and the complexing agent is sodium citrate: the concentration of the complexing agent in the plating solution is 10g/L, the buffer agent is 20g/L of ammonium chloride, the pH regulator is ammonia water, the dosage of the ammonia water is 30ml, and the reducer is DMAB: the concentration of DMAB in the plating solution is 3g/L, and the pH value of the plating solution for electroless plating is 8.0;
(3) Sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder;
the vacuum heat treatment comprises a low-temperature heat treatment and a high-temperature heat treatment which are sequentially carried out, wherein the temperature of the low-temperature heat treatment is 500 ℃, the time of the low-temperature heat treatment is 2 hours, the temperature of the high-temperature heat treatment is 870 ℃, and the time of the high-temperature heat treatment is 4 hours;
wherein the step of controlling oxidation is: paving the powder obtained by the vacuum heat treatment on a ceramic plate; then placing the ceramic plate filled with the powder into a vacuum device, pumping the pressure in the vacuum device to be less than or equal to 10 < -3 > Pa, controlling the partial pressure of oxygen and argon to be 0.3% according to a certain proportion, slowly introducing the oxygen and argon into the vacuum device to control the oxidization, and controlling the oxidization temperature to be 650 ℃ and the time to be 10 hours.
Test example 1
The modified carbonyl iron powder prepared in example 1 was pressed into a coaxial ring, and the sample was tested for room temperature dielectric properties using a vector network analyzerThe energy and magnetic properties, and then deducing the wave absorbing property of the sample. Through test, the wave absorbing performance R of the powder pressed sample with the thickness of 0.4mm L <-5dB, bandwidth of 3.2GHz.
Test example 2
The modified carbonyl iron powder prepared in example 2 is pressed into a coaxial ring, and the normal temperature dielectric property and magnetic property of the sample are tested by adopting a vector network analysis instrument, and then the wave absorption property of the sample is deduced. Tested, 1.2mm sample, R under X wave band (8.2-12.4 GHz) L The maximum is-31 dB, and the bandwidth is 8.2-12.4 GHz.
Test example 3
The modified carbonyl iron powder prepared in example 3 is pressed into a coaxial ring, and the normal temperature dielectric property and magnetic property of the sample are tested by adopting a vector network analysis instrument, and then the wave absorbing property of the sample is deduced. The sample was tested to contain 3% P,1.5mm sample test R L The maximum is-45 dB, and the bandwidth is 8.2-12.4 GHz.
Test example 4
The modified carbonyl iron powder prepared in example 4 is pressed into a coaxial ring, and the normal temperature dielectric property and magnetic property of the sample are tested by adopting a vector network analysis instrument, and then the wave absorbing property of the sample is deduced. Through testing, the prepared sample is compared with carbonyl iron powder which is oxidized for 50 hours at 300 ℃, and the carbonyl iron powder is completely oxidized into Fe 2 O 3 Red, completely lost magnetism; the prepared sample still keeps black and blue and has magnetism.
Test example 5
The modified carbonyl iron powder prepared in example 5 is pressed into a coaxial ring, and the normal temperature dielectric property and magnetic property of the sample are tested by adopting a vector network analysis instrument, and then the wave absorption property of the sample is deduced. The test shows that the Co and Ni content on the surface of the sample is about 23 wt%.
From the above test examples, it can be seen that the present invention can provide a modified carbonyl iron powder containing one or more elements of Ni, co, cu, sn, in, ag, au, pt, rh, pd, ir, W, mo, zn, si and the like, and a binary phase or a ternary phase of high performance can be obtained depending on the reaction of Fe with other elements. And then by controlling the oxygen partial pressure, a proper, compact and high-bonding-strength surface main oxide film can be directionally obtained, the defect that carbonyl iron powder is not corrosion-resistant is greatly improved, and the electromagnetic performance of the carbonyl iron powder is stabilized as much as possible, so that the carbonyl iron powder can be used for a wave-absorbing material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the modified carbonyl iron powder comprises the following steps:
(1) Performing surface activation on carbonyl iron powder to obtain pretreated carbonyl iron powder;
(2) Performing chemical plating on the pretreated carbonyl iron powder obtained in the step (1) to obtain composite carbonyl iron powder;
(3) And (3) sequentially carrying out vacuum heat treatment and controlled oxidation on the composite carbonyl iron powder obtained in the step (2) to obtain modified carbonyl iron powder.
2. The method for producing a modified carbonyl iron powder according to claim 1, wherein the surface activation in step (1) comprises: and etching carbonyl iron powder in the etching solution.
3. The method for producing a modified carbonyl iron powder as claimed in claim 2, characterized in that the etching solution has a pH of 1-3.
4. The method for producing a modified carbonyl iron powder according to claim 1, wherein the electroless plated metal in the step (2) includes one or more of Ni, co, cu, sn, in, ag, au, pt, rh, pd, ir, W, mo and Zn.
5. The method for producing a modified carbonyl iron powder according to claim 1, wherein the vacuum heat treatment in step (3) comprises a low-temperature heat treatment and a high-temperature heat treatment performed in this order.
6. The method for producing a modified carbonyl iron powder according to claim 5, characterized in that the low-temperature heat treatment is carried out at a temperature of 500 ℃ to 650 ℃; the low-temperature heat treatment time is 2-6 h.
7. The method for producing a modified carbonyl iron powder according to claim 5, characterized in that the high temperature heat treatment temperature is 800 ℃ to 950 ℃; the high-temperature heat treatment time is 4-8 hours.
8. The method for producing a modified carbonyl iron powder according to claim 1, wherein the partial pressure of oxygen in the oxidation is controlled to be 0.3% to 8% in the step (3).
9. The modified carbonyl iron powder prepared by the preparation method of any one of claims 1 to 8, which comprises carbonyl iron powder, a transition alloy layer coated on the surface of the carbonyl iron powder, a metal coating coated on the surface of the transition alloy layer and an oxide film coated on the surface of the metal coating.
10. The use of the modified carbonyl iron powder of claim 9 in a wave absorbing material.
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