CN101692364B - One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof - Google Patents
One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof Download PDFInfo
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- CN101692364B CN101692364B CN200910093537A CN200910093537A CN101692364B CN 101692364 B CN101692364 B CN 101692364B CN 200910093537 A CN200910093537 A CN 200910093537A CN 200910093537 A CN200910093537 A CN 200910093537A CN 101692364 B CN101692364 B CN 101692364B
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Abstract
The invention provides a one-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and a preparation method thereof. The material has a composite structure that hard magnetic nano-tubes prepared from hard magnetic phase FePt or CoPt alloy are coated with soft magnetic nano-wires prepared from soft magnetic phase pure metals including Fe, Co and Ni or binary and ternary alloy, wherein, the diameter of the one-dimensional permanent magnetic nano-material is 10nm to 220nm; the diameter of the soft magnetic phase nano-wires is 4nm to 60nm; and the wall thickness of the hard magnetic phase nano-tubes is 3nm to 80nm. The preparation method of the material comprises the following steps: firstly, preparing the hard magnetic alloy nano-tubes in a porous anodic alumina template by using the template wetting method; and then, growing the soft magnetic nano-wires in the nano-tubes by using the electrochemical deposition method. The invention has the advantages that the size of the one-dimensional permanent magnetic nano-material is controllable and the preparation method is simple.
Description
Technical field
The invention belongs to the nano material preparation technical field, particularly provide a kind of Hard Magnetic pipe to coat soft magnetism line style 1-dimention nano permanent magnetic material and preparation method thereof, be applicable to that the Hard Magnetic pipe coats the preparation of soft magnetism line style 1-dimention nano permanent magnetic material.
Background technology
The magnetic-coupled main application of soft or hard is to make high performance permanent magnetic material; 1991; E.F.Kneller etc. have proposed the new principle of preparation permanent magnetic material, when soft magnetic material with nanoscale and hard magnetic material formation composite material, will produce exchange-coupling interaction; Impel the remanent magnetism enhancement effect to occur, produce high magnetic energy product.This nanometer exchange coupling permanent magnet be considered to develop the 4th generation permanent magnetism the important channel.Permanent magnet requires big as far as possible coercive force and saturation magnetization, though the coercive force of hard magnetic material is bigger, its saturation magnetization is lower than soft magnetic material.Hard Magnetic has high coercive force mutually in the exchange-spring, and soft magnetism has high saturation magnetization mutually, and they are combined, and can obtain well behaved permanent magnetic material.The main method of preparation nanometer exchange coupling permanent magnet is a melt-quenching method at present.Molten alloy ingot casting and obtain amorphous thin ribbon with water-cooled copper roller fast quenching melt at first, then, annealing " nature " is at a certain temperature separated out and is comprised permanent magnetism phase and the soft magnetism nano structural material of particle mutually.But the maximum magnetic energy product of the nanometer exchange coupling permanent magnet that experimentally makes is more much lower than the theory expectation, therefore, develops new technology of preparing, and preparing nanometer exchange coupling material through artificial synthesis is the key that improves maximum magnetic energy product.At present the artificial composite structure of preparation mainly be through the method preparation of sputter or extension hard/soft magnetism duplicature or multilayer film; Comprise NdFeB/Fe, SmCo/Fe, FePt/Fe etc.; Equipment needed thereby is comparatively expensive usually; And prepared material only therein one dimension be of a size of nanoscale, be unfavorable for the requirement of following device miniaturization, the trend of current device miniaturization also strides forward the proposition requirements at the higher level to permanent magnetic material towards small scale more.
Obtain good permanent magnetism performance and adopt two kinds of methods usually, a kind of is the material with big magnetocrystalline anisotropy, and another kind is the material with big shape anisotropy.Through artificial design, make material have big shape anisotropy simultaneously with big magnetocrystalline anisotropy, can better bring into play the permanent magnetism performance of material.Outside the one dimension soft magnetic material, coat the hard magnetic layer material, can promote the saturation magnetization of material, increase magnetic energy product.And according to the Slater-Pauling curve, ferrocobalt had the maximum magnetization at about 30% o'clock at cobalt content, and this is the material that has the maximum saturation magnetization in present transition metal of finding and the alloy.
Summary of the invention
The objective of the invention is to propose a kind of Hard Magnetic pipe and coat soft magnetism line style 1-dimention nano permanent magnetic material and preparation method thereof, the controllable size of 1-dimention nano permanent magnetic material, the preparation method is simple and preparation cost is lower, but also has characteristics such as high-coercive force, high-performance.
According to the object of the invention; The solution that we proposed is; Adopt the magnetic-coupled accurate 1-dimention nano coaxial cable of soft or hard, outside the magnetocrystalline anisotropy of material, increased shape anisotropy again, simultaneously because the exchange-coupling interaction of soft or hard magnetic storeroom; Under the situation that coercive force not too reduces, increase the saturation magnetization of material greatly, thereby improve the magnetic property of material.Material is made up of inner filamentary material and outer tubular material, inner Fe, Co, the Ni metal or alloy soft magnetism nanotube of coating, and outside magnetic core is made up of one dimension Hard Magnetic nano wires such as FePt, CoPt.
The preparation method of exchange-spring nano coaxial cable of the present invention is, adopts the electrochemical anodic oxidation method to prepare porous alumina formwork earlier, and through controlled oxidation voltage, hole diameter can be regulated and control.The back adopts the template infusion method around the template hole, to generate Fe
xCo
yNi
(1-x-y)Alloy nanotube, through the electrochemical deposition method Hard Magnetic nano wire of in pipe, growing, preparation technology is then:
A. porous alumina formwork is immersed in the chloroplatinic acid and frerrous chloride mixed solution or chloroplatinic acid and cobalt chloride mixed solution that configures; The shared molar percentage of chloroplatinic acid in mixed solution is 40%～60%; Soak time is 10～60 minutes; Immersion process can not add ultrasonic wave, also can put into supersonic wave cleaning machine ultrasonic 3～60 minutes.
B. put into quartz ampoule after template being taken out, 400 ℃～600 ℃ were reduced 1～5 hour in hydrogen atmosphere, generated FePt or CoPt nanotube; For a change the nanotube wall thickness can repeat A, B process 1～10 time.
C. the foraminous die plate that is loaded with FePt or CoPt nanotube as secondary template, through being electrochemically-deposited in the Fe that grows in the hole, Co, Ni elemental metals or binary, ternary alloy nano line, electrolyte is Fe SO
4, CoSO
4, NiSO
4And H
3BO
3, ascorbic acid mixed solution, wherein H
3BO concentration is 3g/L～45g/L; Ascorbic acid adds when in solution, containing ferrous ion, and adding concentration is 0.2g/L～3g g/L; The slaine of being selected for use assigns to confirm according to required one-tenth; Can select Fe SO
4Or NiSO
4In a kind of, also can be Fe SO
4, CoSO
4, NiSO
4Two or three mixed solution in three kinds, Fe SO
4Mol ratio in slaine is 0～90%, CoSO
4Mol ratio in slaine is 0～70%; Deposition process can not add externally-applied magnetic field, also can add induced magnetic field 100 Oe～5000 Oe, and direction is parallel to the nano wire long axis direction;
D. with the sample for preparing under vacuum 400 ℃～800 ℃ handled 30～100 minutes; Simultaneously also can add a magnetic field, externally-applied magnetic field 100 Oe～5000 Oe, direction is parallel to the nano wire long axis direction.
Characteristics of the present invention are: prepare a kind of novel nanometer permanent magnetism one-dimensional material, be different from original one-dimensional magnetic material, this material is theoretical according to exchange-spring, adopts Hard Magnetic phase nanotube to coat soft magnetism phase nanotube and forms coaxial configuration.This kind structure can effectively improve the permanent magnetism performance of material.Hole in the anodic oxidation aluminium formwork that this method adopts is perpendicular to the template surface growth and be arranged parallel to each other, so the prepared exchange-spring coaxial cable array that goes out is also for being arranged in parallel.This array film uses independent one dimension permanent magnetic material after can wholely using or adopt NaOH solution dissolved oxygen aluminum alloy pattern plate.
Description of drawings
Fig. 1. the Hard Magnetic pipe coats soft magnetism line style 1-dimention nano permanent magnetic material sketch map.
Embodiment
Embodiment
With high-purity aluminium flake 400 ℃ of vacuum annealings 4 hours.Aluminium flake after the annealing was put into absolute ethyl alcohol ultrasonic 1 minute, put into 0.3mol/L NaOH after the taking-up ultrasonic 3 minutes, cleaned with deionized water, dried up.The aluminium flake of handling well is put into the logical 1A electric current of absolute ethyl alcohol and perchloric acid mixed liquor (4: 1) carried out electropolishing 1.5 minutes.Put into 0.3mol/L H after aluminium flake take out cleaned
3PO
4Carry out electrochemical oxidation in the solution, oxidation voltage 120V, oxidization time 3 hours obtains porous alumina formwork.Alumina formwork was immersed in the chloroplatinic acid that configures and frerrous chloride (mol ratio 1: the 1) mixed solution about 30 minutes, template is taken out put into the quartz ampoule that is connected with hydrogen, put into 560 ℃ of reductase 12s of tube furnace hour to sample.Repeat to soak reduction process three times.Obtain being embedded in the FePt nanotube in the foraminous die plate.This template is immersed 0.3mol/L FeCl
2, 0.1mol/L H
3BO
3In 0.3g/L ascorbic acid mixed solution, to adopt to exchange 200Hz, the 12V electro-deposition is a graphite electrode to electrode.With the sample for preparing 10
-3Add 2000 Oe magnetic fields in the Pa vacuum and be incubated 30 minutes down at 530 ℃, magnetic direction is perpendicular to the stencil plane direction.Stove is chilled to room temperature, and be hard magnetic linear nano coaxial cable wrapped by soft magnetic tube in the foraminous die plate this moment.
Claims (3)
1. a Hard Magnetic pipe coats soft magnetism line style 1-dimention nano permanent magnetic material; This material is processed nano wire by soft magnetism phase Fe, Co, Ni elemental metals or the FeCo that is combined to form by these elemental metals, FeNi, CoNi bianry alloy or FeCoNi ternary alloy three-partalloy; Process nanotube by hard magnetic phase FePt or CoPt alloy material, form the one dimension composite construction that the Hard Magnetic pipe coats soft magnetic wire; It is characterized in that: the Hard Magnetic nanotube coats the one dimension composite construction of soft magnetism nano wire; The Hard Magnetic nanotube coats the diameter of soft magnetism nanowire-type 1-dimention nano permanent magnetic material at 10nm～220nm; Soft magnetism phase nanowire diameter 4nm～60nm, Hard Magnetic phase nanotube pipe thickness 3nm～80nm.
2. Hard Magnetic pipe according to claim 1 coats soft magnetism line style 1-dimention nano permanent magnetic material, it is characterized in that: Hard Magnetic phase Fe
xPt
1-xOr Co
xPt
1-x0.4≤x≤0.6 wherein, soft magnetism phase Fe
xCo
yNi
(1-x-y)0≤x≤1,0≤y≤0.7 wherein.
3. one kind prepares the method that the said Hard Magnetic pipe of claim 1 coats soft magnetism line style 1-dimention nano permanent magnetic material, it is characterized in that: concrete technology is:
A. porous alumina formwork is immersed in the chloroplatinic acid and frerrous chloride mixed solution or chloroplatinic acid and cobalt chloride mixed solution that configures; The shared molar percentage of chloroplatinic acid in mixed solution is 40%～60%; Soak time is 10～60 minutes, perhaps in ultrasonic wave ultrasonic 3～60 minutes;
B. put into quartz ampoule after template being taken out, 400 ℃～600 ℃ were reduced 1～5 hour in hydrogen atmosphere, generated FePt or CoPt nanotube;
C. the foraminous die plate that is loaded with FePt or CoPt nanotube as secondary template, through being electrochemically-deposited in the nano wire of the Fe that grows in the hole, Co, Ni elemental metals or FeCo, FeNi, CoNi bianry alloy or FeCoNi ternary alloy three-partalloy, electrolyte is Fe SO
4, CoSO
4, NiSO
4And H
3BO
3, ascorbic acid mixed solution, wherein H
3BO
3Concentration is 3g/L～45g/L; Ascorbic acid adds when in solution, containing ferrous ion, and interpolation concentration is 0.2g/L～3g/L; The slaine of being selected for use assigns to confirm according to required one-tenth; Select Fe SO
4, CoSO
4Or NiSO
4In a kind of, also can be Fe SO
4, CoSO
4, NiSO
4Two or three mixed solution in three kinds, Fe SO
4Mol ratio in slaine is 0～90%, CoSO
4Mol ratio in slaine is 0～70%; Deposition process can not add externally-applied magnetic field, also can add induced magnetic field 100 Oe～5000 Oe, and direction is parallel to the nano wire long axis direction;
D. with the sample for preparing under vacuum 400 ℃～800 ℃ handled 30～100 minutes; Simultaneously also can add a magnetic field, externally-applied magnetic field 100 Oe～5000 Oe, direction is parallel to the nano wire long axis direction.
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|---|---|---|---|
| CN200910093537A CN101692364B (en) | 2009-10-12 | 2009-10-12 | One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof |
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|---|---|---|---|
| CN200910093537A CN101692364B (en) | 2009-10-12 | 2009-10-12 | One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof |
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| CN101692364B true CN101692364B (en) | 2012-09-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102233432B (en) * | 2010-04-22 | 2012-11-07 | 吉林师范大学 | Preparation method of L10-phase CoPt nanoparticles |
| CN102021654B (en) * | 2010-12-06 | 2012-04-25 | 皖南医学院 | Method for preparing magnetic nanotube |
| DE102012204083A1 (en) * | 2012-03-15 | 2013-09-19 | Siemens Aktiengesellschaft | Nanoparticles, permanent magnet, motor and generator |
| DE102013221828A1 (en) * | 2013-10-28 | 2015-04-30 | Siemens Aktiengesellschaft | Nanoscale magnetic composite for high-performance permanent magnets |
| KR102135375B1 (en) * | 2014-11-21 | 2020-07-17 | 엘지전자 주식회사 | Magneto-dielectric composite material for high frequency antenna substrate and manufacturing method of the same |
| CN105132954B (en) * | 2015-08-20 | 2017-08-01 | 河北工业大学 | The preparation method of Sm Co/Fe Co systems two-phase coupling Magnetic Nanowire Arrays |
| CN105112958B (en) * | 2015-08-25 | 2017-09-26 | 中山大学 | A kind of method for going alloyage to obtain nano-porous silver loaded on base material |
| CN105742030B (en) * | 2016-03-08 | 2018-05-22 | 佛山市程显科技有限公司 | A kind of manufacturing method of the E-type magnetic core of transformer and its transformer |
| CN115637394B (en) * | 2022-10-21 | 2023-11-07 | 西北工业大学 | Cobalt-reinforced iron-nickel-based hard magnetic alloy and preparation method thereof |
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|---|---|---|---|---|
| CN1529330A (en) * | 2003-09-29 | 2004-09-15 | 南京大学 | Iron-cobalt alloy nano linear array permanent-magnetic film material and its preparation |
| CN1621338A (en) * | 2004-12-17 | 2005-06-01 | 清华大学 | Synthesis method of iron nanotube array |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529330A (en) * | 2003-09-29 | 2004-09-15 | 南京大学 | Iron-cobalt alloy nano linear array permanent-magnetic film material and its preparation |
| CN1621338A (en) * | 2004-12-17 | 2005-06-01 | 清华大学 | Synthesis method of iron nanotube array |
Non-Patent Citations (2)
| Title |
|---|
| Y.C. Sui等人.Nanotube magnetism.《APPLIED PHYSICS LETTERS 》.2004,第84卷(第9期), * |
| 王子军等人.硬磁/软磁交换弹簧多层膜的研究进展.《材料导报》.2006,第20卷(第7期), * |
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