CN1286126C - Iron-cobalt alloy nano linear array permanent-magnetic film material and its preparation - Google Patents
Iron-cobalt alloy nano linear array permanent-magnetic film material and its preparation Download PDFInfo
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- CN1286126C CN1286126C CN03158372.5A CN03158372A CN1286126C CN 1286126 C CN1286126 C CN 1286126C CN 03158372 A CN03158372 A CN 03158372A CN 1286126 C CN1286126 C CN 1286126C
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- iron
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- cobalt alloy
- film material
- nano linear
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 18
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002070 nanowire Substances 0.000 claims description 33
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000009415 formwork Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract 4
- 238000003491 array Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000005389 magnetism Effects 0.000 description 9
- 239000010409 thin film Substances 0.000 description 7
- 230000003026 anti-oxygenic effect Effects 0.000 description 6
- 230000005415 magnetization Effects 0.000 description 6
- 238000005234 chemical deposition Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Thin Magnetic Films (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
The present invention relates to an iron-cobalt alloy nano linear array permanent magnetic film material. Iron-cobalt alloy nano linear arrays are deposited in electrochemistry anodized alumina nano hole mould plates in an electrochemistry mode, wherein the iron-cobalt alloy nano linear diameter is 10 to 50 nm, and the composition of iron-cobalt alloy is Co<x>Fe<1-x>, wherein x is more than or equal to 0.02 and less than or equal to 0.60. The present invention uses the electrochemistry anodized method for preparing the alumina nano hole mould plates and uses the methods of iron-cobalt alloy nano linear array deposition in an electrochemistry mode and low temperature annealing to obtain iron-cobalt alloy nano linear array permanent magnet film materials with high performance. Especially when the cobalt content is 30 to 40% and the nano linear diameter is 10 to 22 nm, the performance is the best.
Description
One, technical field
The present invention relates to the composition of a kind of iron-cobalt alloy nano-wire array permanent magnet film material.
Two, background technology
Permanent magnetic thin film can be widely used in fields such as microelectromechanical-systems, integrated-optic device, magnetic head, utilizes permanent magnetic thin film to form micromachine, brake apparatus, micropump and some other device.Along with the microminiaturization of electronic device, the research of permanent magnetic thin film is subjected to extensive concern and develops rapidly.To the permanent magnetic thin film choice criteria is 1) good magnetic performance: big magnetic energy product, high Curie temperature, H
cAnd B
rHas low temperature coefficient.2) can obtain by the way of sputtering sedimentation and chemical deposition, can adopt the way of chemical deposition to obtain at last.3) has good environmental stability: favorable mechanical performance and antioxygenic property.At present, the permanent magnet film material of research mainly comprises rare earth permanent magnet, transition metal permanent magnetism and ferrite permanent-magnet.Rare earth permanent magnet has good permanent magnetism performance, but H
cAnd B
rThe temperature coefficient height, antioxygenic property is poor, and can not adopt the way of chemical deposition to obtain.Though ferrite permanent-magnet has good antioxygenic property, magnetic energy product is on the low side (being lower than 5MGOe), H
cAnd B
rThe temperature coefficient height, and be difficult to adopt the way of chemical deposition to obtain.Transition metal permanent magnetism has good antioxygenic property, can adopt the way of chemical deposition and sputtering sedimentation to obtain, but permanent magnetism performance (being lower than 4MGOe) mostly on the low side, just in Pt-Fe and the research of Pt-Co alloy sputter film, obtained big magnetic energy product (near 40MGOe) in recent years, in permanent magnetic thin film, had a good application prospect.But this permanent magnetic thin film needs a large amount of precious metals pts, costs an arm and a leg, and H
cAnd B
rTemperature coefficient is higher, and this class permanent magnet film material can only use in some specific occasion.
The material that obtains good permanent magnetism performance can pass through two kinds of methods.The one, the material with big magnetocrystalline anisotropy, another kind are the materials with big shape anisotropy.At present, all be to utilize these materials to have big magnetocrystalline anisotropy to the research of permanent magnet film materials such as rare earth permanent magnet above-mentioned, transition metal permanent magnetism and ferrite permanent-magnet, and ignored the permanent magnet film material that utilizes shape anisotropy to obtain.Because nano wire has natural shape anisotropy, its direction of easy axis is generally all along nano wire, if we make the magnetic nanometer array film, just is easy to obtain the magnetization perpendicular to the face direction.We know for its coercive force of the permanent magnetic material with big shape anisotropy and are directly proportional with saturation magnetization.That is to say that saturation magnetization is big more, coercive force is also big more, and the permanent magnetism performance is also good more.According to the Slater-Pauling curve, the saturation magnetization M of ferrocobalt
sIncrease with cobalt atom, be about 30% o'clock magnetization maximum (this is the material that has maximum saturation intensity in present transition metal of finding and the alloy) at cobalt atom, the increase with cobalt reduces then.And have good antioxygenic property, high Curie temperature and low H at about 30% Fe-Co alloy at Co content
c, B
rTemperature coefficient.Therefore, we utilize the shape anisotropy searching not only to have high saturation and magnetic intensity but also have the Fe-Co alloy nano linear array of high-coercive force, by adjusting the shared area of magnetic nanometer and the ratio of whole membrane area, magnetostatic interaction between the research nano wire, we can obtain best permanent magnetism performance, develop a kind of novel permanent magnet film material.
Three, summary of the invention
The objective of the invention is: a kind of novel permanent magnet film material is provided, thereby develops a kind of permanent magnetism function admirable, Curie temperature height, good, the low-cost novel permanent magnetic thin-film material of antioxygenic property.Purpose of the present invention especially provide a kind of in aluminium oxide nano hole template electrochemical deposition iron cobalt nanowire array and make the method for high-performance permanent magnet film material with after annealing.
The object of the present invention is achieved like this: utilize the method for electrochemical anodic oxidation to prepare aluminium oxide nano hole template, the size of controlled oxidation voltage adopts the phosphoric acid reaming, obtains required nano aperture size and pitch of holes.With electrochemical deposition ferrocobalt nano-wire array, the good permanent magnet film material of annealing back obtained performance.Iron-cobalt alloy nano-wire array permanent magnet film material has the alloy Co of following composition
xFe
1-x(0.20≤x≤0.60).Its preparation method is: with electrochemical deposition method the ferrocobalt nano-wire array is deposited in the aluminium oxide nano hole template earlier, in low temperature (being lower than 600 ℃) annealing, obtains high performance ferrocobalt nano-wire array permanent magnet film material then.The diameter of ferrocobalt nano wire is at 10nm～50nm, and the spacing between the ferrocobalt nano wire is generally at 30nm～70nm.
Characteristics of the present invention are: utilize the method for electrochemical anodic oxidation to prepare aluminium oxide nano hole template, with electrochemical deposition ferrocobalt nano-wire array and stress relief annealed method, obtained high performance ferrocobalt nano-wire array permanent magnet film material.Especially the content at cobalt is 30%～40%, and when nanowire diameter was 10nm～22nm, nanometer line ordered array can obtain the coercive force of big vertical face, H
c(⊥)=and 2.7kOe～2.9kOe, after 300 ℃～600 ℃ annealing, coercive force H
cBe increased to 3.3kOe～3.8kOe.The ratio of nano wire and aluminium oxide area occupied on the adjusting face, the magnetic energy product of permanent magnet film material can reach more than the 6MGOe.Not special agreement of the time of annealing is generally got the 15-60 branch.
Analyze phase structure with X-ray diffractometer.Adopt vibrating specimen magnetometer to measure magnetic performance.ESEM carries out the nano wire constituent analysis, and transmission electron microscope carries out the nano wire morphology observation.As an example, Fe
0.69Co
0.31Alloy nano-wire array measurement result as shown in the figure.
Four, description of drawings
Fig. 1 is the transmission electron microscope photo of the anodised alumina formwork of 15V.Pitch of holes is about 40nm, and the aperture is about 20nm.
Fig. 2 is Fe
0.69Co
0.31The X-ray diffraction spectrum of alloy nano linear array, (a) electro-deposition attitude (b) was annealed 20 minutes at 550 ℃ after the electro-deposition.
Fig. 3 dissolves Fe behind the aluminium oxide
0.69Co
0.31The transmission electron microscope photo of alloy nano-wire, nanowire diameter is about 20nm.
Fig. 4 Fe
0.69Co
0.31The alloy nano linear array is at the magnetic hysteresis loop of 550 ℃ of annealing after 20 minutes, (a) the vertical face of externally-applied magnetic field, its coercive force is the remanence ratio of coercive force with the vertical face of vertical face with remanence ratio, (b) the parallel face of externally-applied magnetic field, its coercive force is the remanence ratio of coercive force with the parallel face of parallel face with remanence ratio.
Five, embodiment
The invention will be further described below in conjunction with accompanying drawing and by embodiment:
Iron-cobalt alloy Co
xFe
1-x(0.20≤x≤0.60) prescription has certain limit, and especially with the scope preparation of 0.25≤x≤0.40, the ratio of the performance of this ratio and cost is most economical in the present invention, does not have significantly difference on the performance.
The present invention is with following method manufacturing: the method with electrochemical anodic oxidation prepares aluminium oxide nano hole template, and electrolyte is the aqueous sulfuric acid of 2%-15%, and voltage is 10V～27V, adopts the phosphoric acid reaming.As template, electric depositing solution is the aqueous solution that contains iron ion and cobalt ions with the aluminium oxide of nano aperture, obtains Co by the AC electrochemical deposition
xFe
1-x(0.20≤x≤0.60) alloy nano linear array is with after annealing.Electric depositing solution is the aqueous sulfuric acid that contains iron ion and cobalt ions, iron-cobalt alloy Co
xFe
1-x(0.20≤x≤0.60) prescription realizes recently that by the mole of the hydrochlorate of iron and cobalt in fact alloy composition can slightly change.The solution of iron ion and cobalt ions is generally inorganic salt solution, as sulfate (ferrous) etc., can certainly be organic acid molysite or cobalt salt, can be mixed with solution.All at room temperature condition or slightly heat and all can.At low temperature (being lower than 600 ℃) annealing iron-cobalt alloy nano-wire array, obtain high performance ferrocobalt nano wire permanent magnet film material then.Prior art can provide the alumina formwork of different nano aperture, and the nanowire diameter that the diameter difference of nano aperture obtains is also different, certainly and the time of electrochemical process difference is also arranged, it is more excellent at 15nm～25nm generally to get nanowire diameter.
With the actual Co that obtains
0.31Fe
0.69Voltage is the 15V anodic oxidation, and annealing was the example discussion in 20 minutes under 550 ℃ of temperature:
(1) structure of alumina formwork: the nano-pore spacing is 40nm, and the aperture is 20nm, and the shared area of hole is 19.6% of a whole film size.
(2) crystal structure of iron-cobalt alloy and micro-structural: iron-cobalt alloy has body-centered cubic structure, and the parallel nanowires direction has＜and 110〉structure.Nanowire diameter on average is about 20nm, and length on average is about more than the 2 μ m.The filling rate that hole is filled into the FeCo alloy nano-wire is about 95%.
(3) magnetic:
(i) the vertical face of nano wire direction of easy axis (being parallel nanowires), the remanence ratio (M of vertical face direction
r/ M
s) be higher than more than 90% annealing back remanence ratio (M
r/ M
s) be 95%.
The (ii) coercive force H of the vertical face of nanometer line ordered array
c(⊥)=and 2.7kOe, after the annealing, coercive force H
c(⊥) be increased to 3.6kOe, M
r/ M
sBe 95%.Ratio and block Co according to magnetic nanometer area occupied on whole face of filling
31Fe
69The saturation magnetization of alloy, the magnetic energy product that can obtain the nanometer line ordered array film is higher than 6MGOe.
(iii) Co
0.20Fe
0.8And Co
0.6Fe
0.4The magnetic property of nanometer line ordered array is lower than the foregoing description.
Claims (1)
1, iron-cobalt alloy nano-wire array permanent magnet film material, the ferrocobalt nano-wire array that it is characterized in that electrochemical deposition in the aluminium oxide nano hole template of electrochemical anodic oxidation, the diameter of nano aperture alumina formwork is at 10nm～22nm, ferrocobalt nanowire length average out to 2 μ m, the nano-pore spacing is 40nm～50nm, the alloy Co that iron-cobalt alloy is formed
xFe
1-x0.30≤x≤0.40.
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| CN1286126C true CN1286126C (en) | 2006-11-22 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100428376C (en) * | 2005-08-23 | 2008-10-22 | 兰州大学 | Method for controlling magnetic material magnetic parameter temperature stability and material |
| CN100369703C (en) * | 2006-03-28 | 2008-02-20 | 华中师范大学 | Fe nanowire and preparation method thereof |
| CN101692364B (en) * | 2009-10-12 | 2012-09-05 | 钢铁研究总院 | One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof |
| CN102732963B (en) * | 2011-04-15 | 2015-03-04 | 中国科学技术大学 | Preparation method of monocrystalline metal nanowire array based on alumina template |
| CN102543357B (en) * | 2012-01-16 | 2013-05-29 | 兰州大学 | Material with giant magneto-impedance effect and preparation method thereof |
| CN103882479B (en) * | 2014-02-17 | 2016-09-21 | 瑞安市浙工大技术转移中心 | Preparation method with the magnetic alloy nano wire of diameter gradient |
| CN103882489B (en) * | 2014-02-17 | 2017-01-18 | 瑞安市浙工大技术转移中心 | Preparation method of magnetic alloy nanowire with diameter gradient |
| CN104846411B (en) * | 2015-04-27 | 2017-08-25 | 北京航空航天大学 | The method and its product of flower-like nanometer metal cobalt are prepared using anodic oxidation aluminium formwork |
| CN108597710B (en) * | 2018-04-13 | 2019-08-30 | 中国计量大学 | A kind of preparation method of samarium iron nitrogen magnetic nano-array |
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