CN109267101A - A kind of ultra-fine magnetic metallic powder and preparation method thereof - Google Patents
A kind of ultra-fine magnetic metallic powder and preparation method thereof Download PDFInfo
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- CN109267101A CN109267101A CN201810952921.6A CN201810952921A CN109267101A CN 109267101 A CN109267101 A CN 109267101A CN 201810952921 A CN201810952921 A CN 201810952921A CN 109267101 A CN109267101 A CN 109267101A
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 73
- 239000000843 powder Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 238000004070 electrodeposition Methods 0.000 claims abstract description 52
- 238000002604 ultrasonography Methods 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 5
- 239000006174 pH buffer Substances 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 239000013528 metallic particle Substances 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 20
- 239000008151 electrolyte solution Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000006247 magnetic powder Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 238000011017 operating method Methods 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 229940069328 povidone Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 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
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical group [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides a kind of preparation method of ultra-fine magnetic metallic powder, and the ultra-fine magnetic metallic powder is prepared by pulse-electrodeposition process, comprising the following steps: S1. prepares electrolyte system；S2. electrodeposition process；S3. it post-processes；Wherein, electrolyte system described in step S1 includes electrolyte, pH buffer and dispersing agent；Electrodeposition process described in step S2 carries out under pulsed field, and the pulsed field is ultrasound field or ultrasound field and alternating magnetic field.Pulse-electrodeposition process of the present invention in electrodeposition process by being added pulsed field, magnetic metal particle is set to be detached from cathode before growing up, and emulsion dispersion is completed under special electrolytic solutions system, magnetic metallic powder after completing decentralized processing is recycled with electrolyte, processing is collected outside electrolytic cell, the ultra-fine magnetic metallic powder particle obtained using this method is uniform, and particle size distribution range is narrow, good dispersion.
Description
Technical field
The invention belongs to magnetic nanometer powder preparation technical fields, more particularly, to a kind of ultra-fine magnetic metallic powder
And preparation method thereof.
Background technique
Ultra-fine Magnaglo shows the unique physics different from conventional magnetic material, chemistry as a kind of new material
And electromagnetic property, and have a wide range of applications in fields such as machinery, electronics, optics, magnetics, chemistry and biologies, in state of the world
Extremely important effect is played in people's economy and military field.Currently, the ultra-fine common preparation method of magnetic particle has gas phase
Reaction method, coprecipitation, Hydrolyze method and electrodeposition process etc..
Wherein, gas-phase reaction method be using compound steam chemical reaction a kind of method, though this method can synthesize compared with
Good nanometer powder, but it is ineffective for preparing not volatile substance；Co-electrodeposition method is dissolved in water using various
Substance, it is reacted to generate undissolved hydroxide, carbonate, sulfate etc., then heated decomposition generation ultra-micro powder, this side
Though method is simple and easy, that there are impurity is more for obtained ultra-micro powder, reunites the problems such as serious, and for certain metal simple-substances
Preparation be not easy to realize；Hydrolyze method is high-purity ultra-micro powder needed for being directly separated manufacture from the solution of substance, due to making
With the organo-metallic compound needed when Hydrolyze method by a large amount of valuableness, lead to that increased production cost, and there is pollution environment, instead
The problems such as answering process slow；And electrodeposition process refers to that metal or alloy is electric from its compound water solution, non-aqueous solution or fused salt
The process of chemical deposition, is compared with other methods, and electrodeposition process is with easy to operate, equipment is simple, low energy consumption and application range
The features such as wide, therefore, electrodeposition process, become the research hotspot for preparing nano-magnetic powder.
Iron powder, nickel powder and copper powder and its composite material are prepared frequently with electrodeposition process in the prior art, however, existing electricity is heavy
Frequently with acidic electrolysis bath when area method prepares iron powder or nickel powder, the iron powder or nickel powder made is dissolved in acidic electrolysis bath, from
And cause iron powder or nickel powder output capacity very low, it generally can only achieve 25% or so, the prior art is preparing nickel using electrodeposition process
When powder, it can also cooperate addition ultrasound field, however the nickel powder granularity individually using ultrasound field preparation is larger, is unable to get ultra-fine
Powder；And ultra-fine magnetic composite is prepared using electrodeposition process at present and needs to carry out complicated substrate pretreatment, and phase is added
The nano particle answered can just obtain nano-scale magnetic metal powder, and obtained magnetic metallic powder is adhered on cathode plate, need
Artificial hand collects product, and more product impurity, low yield, preparation process complexity, process is led to problems such as to be difficult to control.
Summary of the invention
Technical deficiency existing for preparation method for existing ultrafine particle, new the purpose of the present invention is to provide one kind
The preparation method of ultra-fine magnetic metallic powder prepares nanometer magnetic metal powder, this method preparation using pulse-electrodeposition process
Product output rate and degree of purity it is high, have the characteristics that simple process, easily controllable, pollution-free.
Another object of the present invention is to provide a kind of ultra-fine magnetic metallic powders.The ultra-fine magnetic metallic powder particle is equal
Even, particle size distribution range is narrow, good dispersion.
The technical solution adopted is as follows:
A kind of preparation method of ultra-fine magnetic metallic powder, the ultra-fine magnetic metallic powder is by pulse-electro-deposition legal system
Standby to form, the preparation method comprises the following steps:
S1. electrolyte system is prepared；
S2. electrodeposition process: preparing anode, cathode, is placed in the electrolyte system of step S1 preparation, under pulsed field
Carry out electro-deposition；
S3. it post-processes: step S2 being passed through into the metallic particles that electro-deposition generates, cathode is detached under pulse field action, and
Decentralized processing is completed in the electrolytic solution, is collected in the cyclic process of electrolyte, and ultra-fine magnetic metallic powder is obtained；
Wherein, electrolyte system described in step S1 includes electrolyte, pH buffer and dispersing agent；The pulsed field is ultrasound
Wave field or ultrasound field and alternating electric field.
Further, the magnetic metal is any one in iron, cobalt, nickel and its alloy.
The present invention mainly utilizes pulse-electrodeposition process to prepare ultra-fine magnetic metallic powder, using specific electrolyte system,
Under the system of constant dc, the metal ion in solution obtains electron discharge on cathode plate and is reduced to metallic atom,
It is detached from cathode under the action of pulsed field, and completes decentralized processing in the electrolytic solution, is collected in the cyclic process of electrolyte,
Obtain ultra-fine magnetic metallic powder.
Further, the electrolyte is at least one of the sulfate of metal, chlorate, in the electrolyte metal from
The concentration of son is 0.5~2mol/L.
In order to enhance the stability and electric conductivity of solution, further, the electrolyte also contains ammonium sulfate, described
The concentration of ammonium sulfate is 0~0.8mol/L.
Further, the pH buffer is boric acid, ammonium salt, acetate, any one in citrate.
Further, the concentration of pH buffer is 5~10g/L in the electrolyte system.
Further, the dispersing agent is povidone, thiocarbamide, γ-aminopropyl triethoxysilane, dodecyl sulphate
At least one of sodium.
Further, the concentration of dispersing agent is 0.5~12g/L in the electrolyte system.
The present invention uses specific dispersing agent, emulsified in pulse field action, carries out surface to particle first and is modified, makes it
Surface covers one layer of polymeric, effectively controls the nucleating growth of particle, secondly can also improve the distribution of microcosmic electric current in solution, with
Reach the dispersibility for improving electrolyte solution, to obtain uniform nano metal powder；On the other hand, the particle made
Dispersity is kept in the solution, to prevent from mutually assembling between the fine particle being precipitated in deposition process, is uniformly coated on
The surface of particle, the effective size for controlling particle, to reach Nano grade.
Further, the frequency of the ultrasound field is 20~40KHZ, and power is 50~600W.
Further, the frequency of the alternating electric field is 0~10KHz.
Pulsed field of the invention is individual ultrasound field or ultrasound field and alternating magnetic field, wherein ultrasound field can
It is not only able to emulsified dispersed liquid, plays the effect of mass transmitting for accelerating electrolyte, realizes the purpose for accelerating electrolytic speed, moreover it is possible to make cathode
Particle is rapidly separated cathode plate, prevents crystal grain from growing up；Alternating magnetic field is in electrolysis system in magnetic field range, is being detached from particle
It is moved after cathode plate with alternating magnetic field, preferably in conjunction with the dispersing agent after emulsification, completes decentralized processing.
Further, in step S2, using metal plate or metal alloy plate as soluble anode, or with graphite, aluminium for not
Soluble anode, stainless steel or titanium plate are cathode.
In order to be more advantageous to obtain ultra-fine magnetic metallic powder, further, the cathode material surface smoothness is 8 μm
More than.
Further, the technological parameter of the electrodeposition process are as follows: depositing temperature be 10~80 DEG C, sedimentation time be 2~
For 24 hours, for interpolar away from for 30~100mm, pH value is 1.5~4.5, and current density is 100~500A/m2。
A kind of ultra-fine magnetic metallic powder that the preparation method of above-mentioned ultra-fine magnetic metallic powder is prepared.
Compared with prior art, the beneficial effects of the present invention are:
Pulse-electrodeposition process of the present invention in electrodeposition process first by being added ultrasound field or ultrasound field and friendship
Varying magnetic field, while under the special electrolytic solutions system being made into, adhere to the magnetic molecule being precipitated in cathode uniformly
In on cathode plate, it then is detached from cathode under the action of pulsed field, product is obtained by the circulation of electrolyte, what is made is ultra-fine
Magnetic metallic powder particle is uniform, and particle size distribution range is narrow, good dispersion.
The present invention prepares ultra-fine magnetic metallic powder using electrodeposition process under pulsed field, can large-scale continuous production, by
It is fallen in electrolyte in products obtained therefrom, is then collected under the ringing of electrolyte and obtain nanometer magnetic metal powder, kept away
Exempting from the yield for leading to product because artificially collecting product and degree of purity reduces；Ultra-fine magnetic metallic powder is prepared in the present invention
Degree of purity reaches 99.5% or more.
The method of the present invention simple process, reaction condition is mild, easily controllable, and production cost is low, pollution-free.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram for the nano-magnetic iron powder that the embodiment of the present invention 1 is prepared；
Fig. 2 is the X-ray diffractogram for the nano-magnetic nickel powder that the embodiment of the present invention 4 is prepared；
Fig. 3 is the scanning electron microscope (SEM) photograph for the nano-magnetic iron powder that the embodiment of the present invention 1 is prepared；
Fig. 4 is the scanning electron microscope (SEM) photograph for the nano-magnetic iron powder that the embodiment of the present invention 2 is prepared；
Fig. 5 is the scanning electron microscope (SEM) photograph for the nano-magnetic iron powder that the embodiment of the present invention 3 is prepared.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, it is no intended to limit of the invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1
The present embodiment provides a kind of preparation methods of ultra-fine magnetic powder, specifically includes the following steps:
S1. it prepares electrolyte system: configuring ferrous sulfate solution with deionized water, make ferrous ion concentration 1mol/L,
Povidone, thiocarbamide and boric acid is added, making its concentration in electrolyte system is respectively 0.5g/L, 3g/L, 5g/L；
S2. electrodeposition process: using ingot iron as anode, using stainless steel as cathode, cathode material surface smoothness is 9 μ
M is placed in the electrolyte system of step S1 preparation, the electro-deposition 3h under the pulse field action of ultrasound field and alternating magnetic field,
Electrodeposition temperature is 40 DEG C, and the black powder of one layer of uniform and smooth is obtained on cathode plate, and under ultrasound field effect quickly
It is detached from；
Wherein, the frequency of ultrasound field is 20KHz, power 300W, and the frequency of alternating electric field is 5KHz, interpolar away from for
30mm, pH value 1.5, current density 300A/m2。
S3. it post-processes: step S2 being passed through into the black powder particle that electro-deposition generates, yin is detached under pulse field action
Pole, and decentralized processing is completed in the electrolytic solution, it is collected in the cyclic process of electrolyte, obtains black fine powder, i.e.,
Ultra-fine magnetic powder.
Embodiment 2
The present embodiment provides a kind of preparation method of ultra-fine magnetic powder, difference referring to the preparation method of embodiment 1
It is: in step S1, electrolyte system component are as follows: ferrous sulfate 1mol/L, povidone 8g/L, thiocarbamide 2g/L and sodium citrate
5g/L。
Embodiment 3
The present embodiment provides a kind of preparation method of ultra-fine magnetic powder, difference referring to the preparation method of embodiment 1
It is: in step S1, electrolyte system component are as follows: ferrous sulfate 1mol/L, ammonium sulfate 0.8mol/L, lauryl sodium sulfate
12g/L and sodium acetate 5g/L.
Embodiment 4
The present embodiment provides a kind of preparation methods of ultra-fine magnetic nickel powder, specifically includes the following steps:
S1. it prepares electrolyte system: configuring nickel sulfate solution with deionized water, make nickel ion concentration 0.5mol/L, add
Enter lauryl sodium sulfate, γ-aminopropyl triethoxysilane and boric acid, makes its concentration in electrolyte system be respectively
5g/L、12g/L、10g/L。
S2. electrodeposition process: using nickel plate as anode, using titanium plate as cathode, cathode material surface smoothness is 8 μm, is placed
In the electrolyte system of step S1 preparation, the electro-deposition 2h under ultrasound field effect, electrodeposition temperature is 80 DEG C, in cathode plate
On obtain the celadon powder of one layer of uniform and smooth；
Wherein, the frequency of ultrasound field is 20KHz, and power 600W, interpolar is away from for 80mm, pH value 4.5, current density
For 500A/m2。
S3. it post-processes: step S2 being passed through into the celadon powder particle that electro-deposition generates, yin is detached under pulse field action
Pole, and decentralized processing is completed in the electrolytic solution, it is collected in the cyclic process of electrolyte, obtains grey fine powder, i.e.,
Ultra-fine magnetism nickel powder.
Embodiment 5
The present embodiment provides a kind of preparation method of ultra-fine magnetic nickel powder, difference referring to the preparation method of embodiment 4
It is: in step S1, electrolyte system component are as follows: nickel chloride 2mol/L, ammonium sulfate 0.2mol/L, povidone 6g/L, thiocarbamide 8g/
L, ammonium chloride 8g/L；In step S2, using graphite as anode, electrodeposition time 6h, electrodeposition temperature is 50 DEG C.
Embodiment 6
The present embodiment provides a kind of preparation method of ultra-fine magnetic nickel powder, difference referring to the preparation method of embodiment 4
It is: in step S1, electrolyte system component are as follows: nickel chloride 1.5mol/L, ammonium sulfate 0.8mol/L, lauryl sodium sulfate
10g/L, boric acid 6g/L；In step S2, using aluminium as anode, electrodeposition time 10h, electrodeposition temperature is 30 DEG C.
Embodiment 7
The present embodiment provides a kind of preparation methods of ultra-fine magnetic cobalt powder, specifically includes the following steps:
S1. it prepares electrolyte system: configuring cobalt sulfate solution with deionized water, make concentration of cobalt ions 1mol/L, be added
Povidone, thiocarbamide and boric acid, making its concentration in electrolyte system is respectively 0.5g/L, 3g/L, 10g/L；
S2. electrodeposition process: using cobalt plate as anode, using titanium plate as cathode, cathode material surface smoothness is 10 μm, is placed
In the electrolyte system of step S1 preparation, the electro-deposition 12h under the pulse field action of ultrasound field and alternating electric field, electro-deposition
Temperature is 10 DEG C, and the bois de rose powder of one layer of uniform and smooth is obtained on cathode plate；
Wherein, the frequency of ultrasound field is 40KHz, power 50W, and the frequency of alternating magnetic field is 10KHz, interpolar away from for
100mm, pH value 3, current density 100A/m2。
S3. it post-processes: step S2 being passed through into the bois de rose powder particle that electro-deposition generates, yin is detached under pulse field action
Pole, and decentralized processing is completed in the electrolytic solution, it is collected in the cyclic process of electrolyte, obtains grey fine powder, i.e.,
Ultra-fine magnetism cobalt powder.
Embodiment 8
The present embodiment provides a kind of preparation method of ultra-fine magnetic cobalt powder, difference referring to the preparation method of embodiment 7
It is: in step S2, current density 200A/m2。
Embodiment 9
The present embodiment provides a kind of preparation method of ultra-fine magnetic cobalt powder, difference referring to the preparation method of embodiment 7
It is: in step S2, current density 400A/m2。
Comparative example 1
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S1, electrolyte is carbonate.
Comparative example 2
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S1, electrolyte is contained only in electrolyte system, electrolyte is ferrous sulfate.
Comparative example 3
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S1, electrolyte system includes electrolyte and pH buffer.
Comparative example 4
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S2, be not added with pulsed field.
Comparative example 5
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S2, pH value 5.
Comparative example 6
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S2, pH value 1.
Comparative example 7
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S2, current density 50A/m2。
Comparative example 8
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S2, current density 600A/m2。
Comparative example 9
This comparative example provides a kind of preparation method of ultra-fine magnetic powder, with embodiment referring to the operating procedure of embodiment 1
1 the difference is that: in step S2, electrodeposition temperature be 90 DEG C.
X diffraction analysis is carried out to the ultra-fine magnetic metallic powder that embodiment 1 and embodiment 4 are prepared, testing result is shown in
Fig. 1~2.
As shown in Figure 1, the ultra-fine magnetic metallic powder that prepared by embodiment 1 is iron powder, ultra-fine magnetic gold prepared by embodiment 4
Category powder is nickel powder.
Electronic Speculum observation is scanned to the ultra-fine magnetic metal iron powder that Examples 1 to 3 is prepared, testing result is shown in Fig. 3
~5.
By Fig. 3~5 it is found that ultra-fine magnetic metal iron powder is prepared in spherical or near-spherical in Examples 1 to 3, particle is equal
Even, particle size distribution range is narrow, and dispersibility is very well.
Surface microstructure observation is carried out to the ultra-fine Magnaglo that Examples 1 to 9 and comparative example 1~6 are prepared, is put down
Performance detections, the current efficiency such as equal partial size, current efficiency and degree of purity are the yield of preparation method provided by the invention, specifically
It the results are shown in Table 1.
Table 1
By comparative example 1~4 it is found that the present invention mainly utilizes pulse-electrodeposition process to prepare ultra-fine magnetic metallic powder, in conjunction with
Specific electrolyte system is collected in the cyclic process of electrolyte and obtains ultra-fine magnetic metallic powder, avoids because artificially collecting
Product and cause the yield of product and degree of purity to reduce, and metal powder is made to be in preferable spherical or near-spherical；System of the present invention
The standby degree of purity for obtaining ultra-fine magnetic metallic powder reaches 99.5% or more, and current efficiency can reach 80% or more.
By comparative example 5~6 it is found that pH buffer is added in the present invention in the electrolytic solution, make electrolyte in electrodeposition process
PH stable, and electrolyte can be made to be under mild acid conditions, meet the requirement of electrodeposition process, electrodeposition process reacts item
Part is mild, easily controllable, and current efficiency is high.
By comparative example 7~8 it is found that as current density increases, the ion populations to discharge in the unit time on cathode increase
More, the deposition velocity of metal ion is much larger than crystal grain coarsening rate, and the ion populations to discharge in the unit time on cathode are more,
The powder being prepared is thinner, however current density continue increase when, powder diameter variation reduce；The present invention is strict controlled in energy
It is precipitated in the current density range of powder, current efficiency is high in the range, degree of purity is high.
By comparative example 9 it is found that in electrodeposition process when the temperature is excessively high, diffusion velocity increases, grain growth speed also increases
Greatly, cause powder diameter to increase, be unable to get ultra-fine magnetic metallic powder, the present invention selects suitable electrodeposition temperature, at this
At a temperature of obtain and can satisfy the ultra-fine magnetic metallic powder of requirement.
The present invention carries out electro-deposition system under the pulse field action of individual ultrasound field or ultrasound field and alternating magnetic field
Standby ultra-fine magnetic metallic powder, is made into special electrolytic solutions, and the various process parameters of strict control electrodeposition process, makes
The magnetic molecule that cathode is precipitated uniformly is attached on cathode plate, is then detached from cathode under the action of pulsed field, is passed through
The circulation of electrolyte obtains product, and the ultra-fine magnetic metallic powder particle made is uniform, and particle size distribution range is narrow, dispersibility
It is good.
Obviously, above-described embodiment is only intended to clearly illustrate technical solution of the present invention example, and is not
Restriction to embodiments of the present invention.For those of ordinary skill in the art, on the basis of the above description also
It can make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all
Made any modifications, equivalent replacements, and improvements etc. within the spirit and principles in the present invention should be included in right of the present invention and want
Within the protection scope asked.
Claims (10)
1. a kind of preparation method of ultra-fine magnetic metallic powder, which is characterized in that the ultra-fine magnetic metallic powder is by pulse-electricity
Sedimentation is prepared, and the preparation method comprises the following steps:
S1. electrolyte system is prepared；
S2. electrodeposition process: preparing anode, cathode, is placed in the electrolyte system of step S1 preparation, carries out under pulsed field
Electro-deposition；
S3. it post-processes: step S2 being passed through into the metallic particles that electro-deposition generates, cathode is detached under pulse field action, and in electricity
Decentralized processing is completed in solution liquid, is collected in the cyclic process of electrolyte, obtains ultra-fine magnetic metallic powder；
Wherein, electrolyte system described in step S1 includes electrolyte, pH buffer and dispersing agent；Pulsed field described in step S2 is super
Acoustic wavefield or ultrasound field and alternating magnetic field.
2. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that the electrolyte is metal
Sulfate, at least one of chlorate, the concentration of metal ion is 0.5 ~ 2 mol/L in the electrolyte.
3. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that also contain in the electrolyte
There is ammonium sulfate, the concentration of the ammonium sulfate is 0 ~ 0.8 mol/L.
4. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that the pH buffer is boron
Acid, ammonium salt, acetate, any one in citrate.
5. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that the dispersing agent is poly- dimension
At least one of ketone, thiocarbamide, γ-aminopropyl triethoxysilane, lauryl sodium sulfate.
6. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that the frequency of the ultrasound field
Rate is 20 ~ 40 KHZ, and power is 50 ~ 600 W.
7. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that the frequency of the alternating electric field
Rate is 0 ~ 10 KHz.
8. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that in step S2, with metal
Plate or metal alloy plate are soluble anode, or using graphite, aluminium as insolubility anode, and stainless steel or titanium plate are cathode；Institute
Stating cathode material surface smoothness is 8 μm or more.
9. the preparation method of ultra-fine magnetic metallic powder according to claim 1, which is characterized in that the electrodeposition process
Technological parameter are as follows: depositing temperature is 10 ~ 80 DEG C, and sedimentation time is 2 ~ 24 h, interpolar away from being 30 ~ 100 mm, pH value for 1.5 ~
4.5, current density is 100 ~ 500 A/m2。
10. a kind of ultra-fine magnetic that the preparation method such as any one of the claim 1 ~ 9 ultra-fine magnetic metallic powder is prepared
Property metal powder.
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| CN111014722A (en) * | 2020-03-06 | 2020-04-17 | 湖南有色金属职业技术学院 | Method for preparing silver nanoclusters with strong fluorescence emission in soda ash environment |
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