CN101307465A - Method for preparing high entropy alloy magnetic materials - Google Patents
Method for preparing high entropy alloy magnetic materials Download PDFInfo
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- CN101307465A CN101307465A CNA2008100261190A CN200810026119A CN101307465A CN 101307465 A CN101307465 A CN 101307465A CN A2008100261190 A CNA2008100261190 A CN A2008100261190A CN 200810026119 A CN200810026119 A CN 200810026119A CN 101307465 A CN101307465 A CN 101307465A
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Abstract
The invention discloses a method for preparing a high entropy alloy magnetic material. The method adopts a cathode electrodeposited method: an organic system solution containing thulium ions, bismuth ions, iron ions or ferrous ions, cobalt ions, nickel ions and manganese ions is prepared first, and the solution is added with supporting electrolytes; electrodeposit is carried out by taking copper sheets as working electrodes coupled with electric field to obtain the high entropy alloy magnetic material containing thulium, bismuth, iron, cobalt, nickel and manganese. The preparation method of the invention has the advantages of mild condition, simple production process, cheap materials used and high utilization rate, and can be carried out at the normal temperature; moreover, the preparation method belongs to a non-linear process, and by the method, an even coating can form on a matrix with complicated shape by deposition, and the magnetic material obtained has the advantages of soft magnetism as well as permanent magnetism, so that the method has quite high utilization value and good market prospect.
Description
Technical field
The present invention relates to many pivots high-entropy alloy material field, be specifically related to a kind of preparation method who contains the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Background technology
Magneticsubstance is used and is related to every field, and the exploitation of novel magnetic material has important pushing effect to the development of new high-tech material industry.
After Nd-Fe-B the 4th generation permanent magnet material be the key subjects in present scientific research field.Obtain low-symmetry, high magnetocrystalline anisotropy, the permanent magnet material of high energy product is the basic characteristics and the requirement of this research.Simultaneously because the high saturation and magnetic intensity of soft magnetic materials, soft magnetism and permanent magnetism are carried out the permanent magnet material that Compound Machining and then acquisition have the two advantage concurrently at nanoscale has important meaning for the performance requriements that solves type material, has caused scientist and entrepreneur's interest at present.
The alloy of being made up of rare earth element and magnesium-yttrium-transition metal has good magnetic performance.In order to improve the alloy material magnetic performance, can metal alloy or particulate be uniformly dispersed by nano-crystallization, thereby obtain high performance magneticsubstance to reach practical purpose.
Many pivots high-entropy alloy is a kind of new nano material design concept, contains 5 kinds and above element in many pivots high-entropy alloy.High entropy is the characteristic of many pivots alloy, because high entropy effect suppresses the appearance of intermetallic compound, helps to form simple crystallization phases, and makes microstructure tend to nanometer, obtains nano structural material easily.
The preparation method of high-entropy alloy mainly adopts the electric arc melting method at present.The problem that has apparatus expensive and complicated operation causes the material cost height, has hindered application.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of preparation method who contains thulium bismuth iron-cobalt-nickel manganese high entropy alloy magnetic materials is provided, utilize this method can under the condition of gentleness, prepare the high entropy alloy magnetic materials of nanostructure.
To achieve these goals, the present invention adopts following technical scheme:
The preparation method of high entropy alloy magnetic materials of the present invention adopts the cathode electrodeposition method.
Cathode electrodeposition is to utilize the extra electric field effect, at negative electrode generation chemical reaction, makes metal ion in negative electrode generation reduction reaction, and then deposits on matrix.
The concrete steps of cathode electrodeposition law technology scheme of the present invention are:
(1) preparation contains the organic system solution of thulium ion, bismuth ion, iron ion or ferrous ion, cobalt ion, nickel ion and mn ion;
(2) add supporting electrolyte, as working electrode, extra electric field carries out galvanic deposit promptly with copper sheet.
In the above-mentioned steps (1), the bismuth ion volumetric molar concentration is controlled between the 0.002mol/L to 0.01mol/L; Except that bismuth ion, the volumetric molar concentration of other any metal ions is controlled between the 0.002mol/L to 0.03mol/L; Except that bismuth ion, other metal ions are thulium ion (rare earth ion), iron ion, cobalt ion, nickel ion and mn ion or thulium ion (rare earth ion), ferrous ion, cobalt ion, nickel ion and mn ion.
In the above-mentioned steps (2), the supporting electrolyte of adding is an indifferent electrolyte.
In the above-mentioned steps (2), extra electric field is to be reference electrode with the saturated calomel electrode, and the current potential of galvanic deposit is less than-2.7V.
In cathode electrodeposition, the reaction that negative electrode takes place is M
N++ ne=M, deposition process relates to the diffusion and the reallocation of multielement, and the nucleation and the growth of precipitate are suppressed, and make microstructure tend to nanometer and noncrystallineization, help the formation of nanophase.
Compared with prior art, the present invention has following beneficial effect: (1) preparation method of the present invention can carry out at normal temperatures, and production process is simple, and the required investment of plant and instrument is lower; (2) preparation method of the present invention belongs to non-linear process, can deposit on complex-shaped matrix and obtain uniform coating; (3) preparation method of the present invention is raw materials used cheap economical, the utilization ratio height; (4) magneticsubstance of the present invention has soft magnetism, has very high utility value and market outlook.
Description of drawings
Fig. 1 is the Electronic Speculum result of high entropy alloy magnetic materials;
Fig. 2 is the power spectrum result of high entropy alloy magnetic materials.
Embodiment
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.01mol/L thulium ion, 0.002mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.01mol/L thulium ion, 0.002mol/L bismuth ion, 0.01mol/L ferrous ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.002mol/L thulium ion, 0.002mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.03mol/L thulium ion, 0.002mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Embodiment 5
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.01mol/L thulium ion, 0.002mol/L bismuth ion, 0.002mol/L iron ion, 0.002mol/L cobalt ion, 0.002mol/L nickel ion and 0.002mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.01mol/L thulium ion, 0.002mol/L bismuth ion, 0.03mol/L iron ion, 0.03mol/L cobalt ion, 0.03mol/L nickel ion and 0.03mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Embodiment 7
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.01mol/L thulium ion, 0.01mol/L bismuth ion, 0.01mol/L ferrous ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Preparation contains the dimethyl sulfoxide (DMSO) organic system solution of 0.01mol/L thulium ion, 0.01mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Embodiment 9
Preparation contains the dimethyl formamide organic system solution of 0.01mol/L thulium ion, 0.01mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the lithium perchlorate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Preparation contains the dimethyl formamide organic system solution of 0.01mol/L thulium ion, 0.01mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the tetraethyl-ammonium hexafluorophosphate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy nanometer soft magnetic materials of thulium bismuth iron-cobalt-nickel manganese.
Embodiment 11
Preparation contains the dimethyl formamide and the acetonitrile blend organic system solution of 0.01mol/L thulium ion, 0.01mol/L bismuth ion, 0.01mol/L iron ion, 0.01mol/L cobalt ion, 0.01mol/L nickel ion and 0.01mol/L mn ion, the tetraethyl-ammonium hexafluorophosphate that adds 0.3mol/L, with copper sheet as working electrode,-2.7V current potential deposit 5 minutes, can obtain containing the high entropy alloy magnetic materials of thulium bismuth iron-cobalt-nickel manganese.(Electronic Speculum the results are shown in Figure 1, power spectrum the results are shown in Figure 2 and table 1).
The content of each element of table 1 (weight ratio and atom number ratio)
Claims (5)
1, a kind of preparation method of high entropy alloy magnetic materials is characterized in that comprising following steps:
(1) preparation contains the organic system solution of thulium ion, bismuth ion, iron ion or ferrous ion, cobalt ion, nickel ion and mn ion;
(2) add supporting electrolyte, as working electrode, extra electric field carries out galvanic deposit promptly with copper sheet.
2, preparation method according to claim 1 is characterized in that in the step (1), described bismuth ion volumetric molar concentration is 0.002mol/L～0.01mol/L.
3, preparation method according to claim 1 is characterized in that in the step (1), except that bismuth ion, the volumetric molar concentration of other any metal ions is 0.002mol/L～0.03mol/L.
4, preparation method according to claim 1 is characterized in that in the step (2), described supporting electrolyte is an indifferent electrolyte.
5, preparation method according to claim 1 is characterized in that in the step (2), described extra electric field is to be reference electrode with the saturated calomel electrode, and the current potential of galvanic deposit is less than-2.7V.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603287A (en) * | 2016-02-19 | 2016-05-25 | 中原工学院 | Oxide-based high-entropy alloy ceramic binding agent special for PCBN |
| CN105951140A (en) * | 2016-06-08 | 2016-09-21 | 中国计量大学 | Rare earth-free manganese-based permanent magnet electroplating solution and preparation method thereof |
| CN105951125A (en) * | 2016-06-08 | 2016-09-21 | 中国计量大学 | Novel manganese-based magnetic electroplate liquid and preparation method thereof |
| CN105970257A (en) * | 2016-06-30 | 2016-09-28 | 中国计量大学 | Ferrum-manganese-phosphorus magnetic alloy electroplating solution and preparation method thereof |
| CN107675059A (en) * | 2016-07-28 | 2018-02-09 | 龙岩紫荆创新研究院 | Application of the magnetic high-entropy alloy film and preparation method thereof with high-entropy alloy film |
| CN108728876A (en) * | 2018-06-06 | 2018-11-02 | 西南石油大学 | A kind of preparation method of FeCoNiCuMo high-entropy alloys film |
| CN108977855A (en) * | 2018-08-30 | 2018-12-11 | 李鹏 | A kind of preparation method of magnetic material |
-
2008
- 2008-01-29 CN CNA2008100261190A patent/CN101307465A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603287A (en) * | 2016-02-19 | 2016-05-25 | 中原工学院 | Oxide-based high-entropy alloy ceramic binding agent special for PCBN |
| CN105951140A (en) * | 2016-06-08 | 2016-09-21 | 中国计量大学 | Rare earth-free manganese-based permanent magnet electroplating solution and preparation method thereof |
| CN105951125A (en) * | 2016-06-08 | 2016-09-21 | 中国计量大学 | Novel manganese-based magnetic electroplate liquid and preparation method thereof |
| CN105951140B (en) * | 2016-06-08 | 2018-08-17 | 中国计量大学 | Rare earth-free manganese-based permanent magnet electroplating solution and preparation method thereof |
| CN105951125B (en) * | 2016-06-08 | 2018-08-17 | 中国计量大学 | A kind of manganese base magnetism electroplate liquid and preparation method thereof |
| CN105970257A (en) * | 2016-06-30 | 2016-09-28 | 中国计量大学 | Ferrum-manganese-phosphorus magnetic alloy electroplating solution and preparation method thereof |
| CN105970257B (en) * | 2016-06-30 | 2018-12-25 | 中国计量大学 | A kind of iron-manganese-phosphorus magnetic alloy electroplate liquid and preparation method thereof |
| CN107675059A (en) * | 2016-07-28 | 2018-02-09 | 龙岩紫荆创新研究院 | Application of the magnetic high-entropy alloy film and preparation method thereof with high-entropy alloy film |
| CN107675059B (en) * | 2016-07-28 | 2019-06-21 | 龙岩紫荆创新研究院 | Application of the magnetic high-entropy alloy film and preparation method thereof with high-entropy alloy film |
| CN108728876A (en) * | 2018-06-06 | 2018-11-02 | 西南石油大学 | A kind of preparation method of FeCoNiCuMo high-entropy alloys film |
| CN108977855A (en) * | 2018-08-30 | 2018-12-11 | 李鹏 | A kind of preparation method of magnetic material |
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Open date: 20081119 |