CN107460505B - The preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film - Google Patents
The preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film Download PDFInfo
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- 229910017061 Fe Co Inorganic materials 0.000 title claims abstract description 120
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229910000691 Re alloy Inorganic materials 0.000 title claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 62
- 230000008021 deposition Effects 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 239000002070 nanowire Substances 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004471 Glycine Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 40
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 29
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 16
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
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- 239000011668 ascorbic acid Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
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- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
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- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 83
- 238000004070 electrodeposition Methods 0.000 abstract description 16
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- 238000006243 chemical reaction Methods 0.000 abstract description 7
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- 238000005137 deposition process Methods 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
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- 150000001875 compounds Chemical class 0.000 abstract description 3
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- 238000007254 oxidation reaction Methods 0.000 description 38
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 20
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 20
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 20
- 238000005498 polishing Methods 0.000 description 20
- 238000000137 annealing Methods 0.000 description 16
- 239000012530 fluid Substances 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 16
- 235000006408 oxalic acid Nutrition 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 8
- 238000009415 formwork Methods 0.000 description 8
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
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- 230000001590 oxidative effect Effects 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
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- 238000010494 dissociation reaction Methods 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910002546 FeCo Inorganic materials 0.000 description 2
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- -1 rare earth compound Chemical class 0.000 description 2
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- 229910000531 Co alloy Inorganic materials 0.000 description 1
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- 239000012876 carrier material Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
Abstract
The present invention is a kind of preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film.This method is to prepare Tb-Fe-Co nano wire film using the method for electrochemical deposition in aqueous solution, and by the way that glycine to be added in Tb-Fe-Co solution system, glycine and Tb form complex compound, reduction potential is shuffled, increase pH value simultaneously, weakens evolving hydrogen reaction, thus by Tb3+It is restored from solution.Present invention process is simple, and at low cost and success rate is high, and the composition of alloy deposition film can be adjusted by control electrolyte composition ratio and deposition process conditions.
Description
Technical field
Technical solution of the present invention includes the manufacture of multielement rare earth alloy magnetic nanometer film, specifically Tb-
The preparation method of Fe-Co ternary RE alloy magnetic nanometer film.
Background technique
In the up-to-date technology revolution using information, the energy, material as pillar, information-recording material plays very important work
With.It is repeated in recording medium material erasable, magnetic recording media and Magnetooptic recording medium are most wide materials with the most use.Magnetic
Optical memory material is that a kind of magnetic write-in light using Kerr magnetooptical effect reads out record, rewriting, the carrier material for deleting information.
It has converged the advantages of optical storage and magnetic storage, is widely used to national management, military affairs, aerospace, petroleum mineral products, traffic
Etc. needing large-scale data real-time collecting, record, storage and the field of analysis.Remember generally, for information storage magneto-optic
Recording medium material should at least meet following requirement:
(l) stronger Kerr magnetooptical effect.The Kerr magnetooptical effect the strong more is easy to the access of information, and sufficiently large Ke Er turns
Angle so as to read information using Ke Er and Faraday effect, and wipes information by the formation in inverse area.
(2) higher perpendicular magnetic anisotropic；
(3) big coercivity is to provide high storage density.
(4) good uniformity and low surface disturbance；
(5) suitable Curie temperature, Curie temperature Tc is about between the range of 400K-600K；
(6) domain structure has long-time stability；
(7) lower film deposition temperature and high deposition velocity.
Due to the alloy amorphous film Tb-Fe-Co of rare earth-transition race have big magnetic anisotropy, strong ferromagnetic property and
Suitable Curie temperature (500K), is widely paid close attention in terms of magnetooptic recording with storage.On preparation method, generally adopt
It is prepared with physical methods such as vacuum evaporation and magnetron sputterings, but performance due to recording medium film and uniformity are strongly dependent on
The many factors such as sputtering power, target-substrate distance, gas pressure, back end vacuum degree make these methods there are at high cost, low efficiency, sink
The disadvantages of lamination composition is not easy to control.And electrochemical deposition method the biggest advantage is to can by control electrolyte composition and
Deposition process conditions adjust the composition of alloy deposition film, are very suitable to the alloy material of preparation heterogeneity.
Using there are two types of the common solution systems of electrochemical deposition, one is aqueous solution, another kind is ionic liquid.Ion
Liquid refers to the organic liquid substance being composed entirely of ions under room temperature and similar temperature, also referred to as room temperature molten salt.Matching
It first has to prepare ionic liquid when electrolyte processed, chemicals used is then dissolved in the electrolysis that ionic liquid could be made required
Liquid.This liquid must be carried out when preparing in the vacuum drying glove box full of protective gas, it is desirable that ionic liquid cannot
There is the doping of little water, is otherwise easy to cause the failure of an experiment, institute's poor controllability in this way, at high cost, improper high-volume
Production.Again since ionic liquid is room temperature molten salt, viscosity is big, therefore exists and be easy lacking for obstruction AAO form plate hole when depositing
Point.And metal ions in aqueous solution, environmental condition require low, viscosity is small to be not easy to plug, and deionized water raw material is easy to get into
This is low, therefore merits our study.
Currently, electrochemical deposition rare earth alloys carry out mostly in solion, such as Gong Xiaozhong is in low temperature molten salt
Sm-Co nano wire [Gong Xiaozhong, Tang Jiaoning, Li Junqin, etc. rare earth samarium cobalt permanent magnet are prepared for using direct current deposition method in system
The electro-deposition preparation of function alloy film and magnetic performance, China YouSe Acta Metallurgica Sinica, 2007,17 (5), 750-756.], Yang Peixia
Electrochemical deposition is used to be prepared for Co nano wire [Yang Peixia, An Maozhong, Su Caina etc., in ionic liquid Deng in solion
The electro-deposition behavior of cobalt, Acta PhySico-Chimica Sinica, 2008,24 (11): 2032-2036.], what these were prepared in solion receives
Rice noodles shape is generally irregular, and the hole of AAO template is easy to block during the deposition process, under the quality for leading to nano wire film
Drop.Former, to deposit Determination of multiple metal elements in nano wire, the method for being typically employed in alternating deposit in different solutions,
The method that laboratory where the present inventor uses direct current electrochemical deposition, in Sm-Co solution and Fe-Co solution alternately
Deposition is prepared for Sm-Co/Fe-Co biphase line.Although this method can make nano wire become multicomponent alloy nano wire,
It is due to alternating deposit, nano wire uneven components, Sm-Co and Fe-Co are distributed in nano wire at section, to affect film
The raising of performance.
Summary of the invention
It is an object of the present invention to be directed to the deficiency of current multielement rare earth alloy deposition method, a kind of Tb-Fe-Co ternary is provided
The preparation method of rare earth alloy magnetic nanometer film.This method is to be prepared in aqueous solution using the method for electrochemical deposition
The method of Tb-Fe-Co nano wire film, by the way that glycine to be added in Tb-Fe-Co solution system, glycine and Tb form network
Object is closed, reduction potential is shuffled, while increasing pH value, weakens evolving hydrogen reaction, thus by Tb3+It is restored from solution.Method work
Skill is simple, and at low cost and success rate is high, and it is heavy alloy can be adjusted by control electrolyte composition ratio and deposition process conditions
The composition of integrated membrane.
The technical solution of the present invention is as follows:
A kind of preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film, comprising the following steps:
The first step, the processing of AAO template metal spraying
AAO template is put into ion sputtering instrument, using Au as target, sputtering current 10mA, vacuum degree 3x10-2Pa's
Under the conditions of metal spraying 5min~10min, AAO template one side sputter layer of Au atom, Au atomic thickness be 1um~10um；
Second step, Fe-Co deposit the preparation of liquid and Tb-Fe-Co deposition liquid
By frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid (H3BO3), citric acid (C6H8O7) and
Ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Fe-Co alloy/C electrolytic deposition liquid；Deposit each material in liquid
Concentration are as follows: C (FeCl2·4H2O)=0.35mol/L~0.55mol/L, C (CoCl2·6H2O)=0.15mol/L~
0.35mol/L, C (H3BO3)=0.4mol/L~0.6mol/L, C (C6H8O7)=0.05mol/L~0.09mol/L, C (C6H8O6)
=0.01mol/L~0.03mol/L；
By terbium chloride (TbCl3·6H2O), frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid
(H3BO3), glycine (C2H5NO2) and ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Tb-Fe-Co alloy electricity
Solution deposition liquid；Deposit the concentration of each material in liquid are as follows: C (TbCl3·6H2O)=0.4mol/L~1mol/L, C (FeCl2·
4H2O)=0.1mol/L~1mol/L, C (CoCl2·6H2O)=0.1mol/L~1mol/L, C (H3BO3)=0.4mol/L~
0.6mol/L, C (C2H5NO2)=0.25mol/L~0.65mol/L, C (C6H8O6)=0.01mol/L~0.03mol/L；
Third step, the deposition of Tb-Fe-Co multielement rare earth alloy magnetic nanometer
AAO template is mounted in dislodger, is first poured into Fe-Co alloy/C electrolytic deposition liquid in dislodger, with AAO mould
Plate is cathode, and graphite is anode, and energization DC voltage is 2V~3V, and deposition current is 0.5mA~20mA, while using magnetic agitation
Device agitating solution；Energization 10s~60s, in the bottom deposit part Fe-Co bielement nano line of AAO form plate hole, then by Fe-
Co alloy electrolytic deposition liquid is poured out pours into Tb-Fe-Co alloy electrolytic deposition liquid again, and conduction time 0.5h~12h can be prepared by
Tb-Fe-Co alloy nano-wire；
Magnetic agitation rotating speed is 1r/s~5r/s in the third step.
The preparation method of above-mentioned Tb-Fe-Co ternary RE alloy magnetic nanometer film, wherein chemical reagent used is quotient
Purchase gained.
Substantive distinguishing features of the invention are as follows:
Since rare earth element sedimentation potential is lower, there are serious evolving hydrogen reaction, therefore rare earth element in electrodeposition process
Ion from aqueous solution electrodeposition be metal be it is highly difficult, generally can be used shuffle rare earth element evolution or deposition potential method come
Inhibition hydrogen is precipitated and is conducive to the electro-deposition of rare earth.The compound of another aspect rare earth element easily hydrolyzes in aqueous solution,
Complexing agent, stabilizer etc. thus need to be added, select complexing agent appropriate and suitable pH value to inhibit the hydrolysis of rare earth compound,
Make electrolyte is stable to shuffle with rare earth element deposition potential.Therefore for the selection of complexing agent, the adjusting of pH value, deposition voltage
Selection and using certain metal ions induced codeposition effect be the key that realize from aqueous solution electrodeposition rare earth alloy.It arrives
So far, there is no the related skills that deposition Tb-Fe-Co ternary RE alloy in aqueous solution prepares magnetic nanometer film
Art, therefore the present invention is of great significance.
The beneficial effects of the present invention are:
A kind of preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film of the present invention has reality outstanding
Matter feature is as follows: (technical)
1, the present invention when deposition of rare-earth-transition group alloy Tb-Fe-Co magnetic nanometer film, adds in water solution system
Add suitable complexing agent glycine, shuffles the reduction potential of rare-earth metal Tb, to effectively improve the deposition of rare earth ion
Efficiency prepares the relatively high rare earth-transition race complex alloy thin film of content of rare earth.Since pH value size represents H in solution+
Content, so being added to glycine and boric acid in solution, glycine makes pH become larger, and boric acid makes pH become smaller, and boric acid has surely simultaneously
The effect for determining pH value of solution has finally determined glycine and the suitable concentration range of boric acid, C (boric acid)=0.4mol/ through overtesting
L~0.6mol/L, C (glycine)=0.25mol/L~0.65mol/L.
2, the DC voltage that uses of the present invention is 2V~3V, and the migration of ion provides dynamic when voltage is electrochemical deposition
Power, theoretically voltage is bigger, and ionic mobility is higher, and deposition efficiency is higher, but voltage is excessive that will cause deposition rate too fast
And block nano-pore.Tb is heavy rare earth element, and atom is bigger, if voltage is too small, Tb3+There is no enough motivation transfers to hole
In, cause deposition to decline.Through overtesting, present invention determine that the optimum voltage of Tb-Fe-Co ternary alloy nano line deposition is
2V~3V.
3, the present invention is heavy in AAO form plate hole bottom first when depositing Tb-Fe-Co ternary RE alloy magnetic nanometer
The Fe-Co nano wire of 10s~60s is accumulated.Since Fe-Co nano wire is easier to deposit, it can deposit largely receive in a short time
Rice noodles increase the electric conductivity of AAO template, increase electric current when next step Tb-Fe-Co multicomponent alloy nanowire deposition, mention
The high deposition of Tb ion.
A kind of preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film of the present invention have significantly into
It walks as follows: (in performance)
1, the preparation method of Tb-Fe-Co ternary alloy three-partalloy magnetic nanometer film of the present invention is to succeed for the first time in aqueous solution
The method for depositing Tb-Fe-Co ternary RE alloy simultaneously.This method is of less demanding to depositional environment condition, dissolved compound
Deionized water used is cheap and easy to get, greatly reduces cost relative to solion deposition, is suitble to large-scale production.
2, Tb-Fe-Co ternary RE alloy magnetic nanometer film is the selection of good magnetooptical memory material, Mei Yigen
Nano wire is as a magnetic recording point, therefore the order of nano wire affects record and the reading of information.It is prepared by the present invention
Tb-Fe-Co ternary RE alloy nano-wire deposition is high, compact arrangement, high-sequential, the smooth densification of wire body, line footpath uniform one
It causes, convenient for the record of information and reading in application.
3, Tb-Fe-Co ternary RE alloy magnetic nanometer film deposited prepared by the present invention is non crystalline structure, noise
Than relatively low.The major defect of polycrystalline material is to make domain shape chaotic there are a large amount of crystal boundary, is easy to happen the unrestrained anti-of light
It penetrates, thus noise is big, signal-to-noise ratio is low.Tb-Fe-Co ternary RE alloy magnetic nanometer has big coercivity and saturation simultaneously
The intensity of magnetization, higher perpendicular magnetic anisotropy, thus, Tb-Fe-Co ternary RE alloy magnetic nanometer prepared by the present invention is thin
Film is good magnetooptical memory material.
Detailed description of the invention
Fig. 1 is the schematic device of oxidation trough used when preparing anodic oxidation aluminium formwork (AAO template).
Fig. 2 is to carry out the device for removing bottom reactor used when bottom is managed to anodic oxidation aluminium formwork (AAO template) to show
It is intended to.
Fig. 3 is the schematic device of dislodger used when carrying out electrochemical deposition.
Fig. 4 is using Hitachi S-4800 type field emission scanning electron microscope to AAO template made from the embodiment of the present invention 1
FESEM figure: Fig. 4 (a) front elevation；Fig. 4 (b) side view
Fig. 5 is using Hitachi S-4800 type field emission scanning electron microscope to Tb-Fe-Co made from the embodiment of the present invention 1
The FESEM map of multielement rare earth alloy magnetic nanometer film.Fig. 5 (a) nano wire front view；Fig. 5 (b) nano wire side view；
The biggish front view of Fig. 5 (c) nano wire dissociation degree；The side view that Fig. 5 (d) nano wire will be completely dissociated；
Fig. 6 is using Hitachi S-4800 type field emission scanning electron microscope to Tb-Fe-Co made from the embodiment of the present invention 1
The EDS map of multielement rare earth alloy magnetic nanometer film.
Fig. 7 is dilute to the more members of Tb-Fe-Co made from the embodiment of the present invention 1 using Philips PW1700 type X-ray diffractometer
The XRD spectrum of native alloy magnetic nanometer film.
Fig. 8 is using 7407 type vibrating specimen magnetometer of Lake Shore Model to Fe- made from the embodiment of the present invention 1
The VSM map of the magnetic property of Co binary alloy nano line film and Tb-Fe-Co ternary RE alloy magnetic nanometer film: Fig. 8
(a) Fe-Co binary alloy nano line film；Fig. 8 (b) Tb-Fe-Co ternary RE alloy magnetic nanometer film
Specific embodiment
Anodic oxidation aluminium formwork (AAO template) of the present invention is well known materials, and technology of preparing is well-known technique.
Embodiment 1
The first step, aluminium flake pretreatment
By with a thickness of 0.3mm, the high-purity aluminum foil that purity is 99.999%, aluminium flake oxygen is being prevented full of argon gas or nitrogen etc.
It anneals in the protective atmosphere of change, annealing temperature: 500 DEG C of annealings, annealing time: 3h.
The pretreatment such as successively cleaned, remove surface natural oxide film, polishing treatment to the aluminium foil of annealing.
Cleaning: aluminium foil is successively put into acetone and dehydrated alcohol, the ultrasonic cleaner ultrasonic cleaning through 1000w
5min。
Removal surface natural oxide film: the aluminium foil after cleaning is immersed in 15min in the NaOH solution of 10%wt, Zhi Houyong
Deionized water is rinsed well.
Polishing treatment: using graphite as cathode, the aluminium foil of removal surface natural oxide film is anode, using DC voltage 15V
Polishing 5min is carried out in polishing fluid.Polishing fluid configuration proportion is volume ratio VDehydrated alcohol: VPerchloric acid(perchloric acid concentration is 70% to=3:1
wt)。
Second step, the preparation of anodic oxidation aluminium formwork (AAO template)
Aluminium foil is mounted in oxidation trough after pretreatment, is poured into oxalic acid solution and is carried out first time oxidation, aoxidizes for the first time
Aluminium foil afterwards will impregnate 4h in treatment fluid, be mounted in oxidation trough by the aluminium flake impregnated again later, pour into oxalic acid solution
Carry out oxidation for the second time (second is still that the contact surface aoxidized for the first time is contacted with oxalic acid when oxidation).Oxidizing condition:
The oxalic acid solution 300mL of 0.3mol/L, energization DC voltage 40V, 10 DEG C of temperature, oxidization time 4h.The treatment fluid is 6%
The H of wt3PO4The H of solution and 1.8%wt2CrO3The mixed liquor of solution, wherein mass ratio H3PO4Solution: H2CrO3Solution=
10:4.Aluminium foil after second is aoxidized is put into the reactor of bottom, not the one side of oxidation film upward, by the CuCl of saturation2
Solution 0.8mL is added dropwise on aluminium foil, aluminium foil is taken out after reaction, in the H of 5%wt after cleaning up3PO4It is impregnated in solution
The penetrating AAO template in two sides is made in 60min.
Oxidation trough used in the present invention, go the schematic diagram of bottom reactor and dislodger respectively as Fig. 1, as shown in Figures 2 and 3.
As shown in Figure 1, aluminium foil is mounted in oxidation trough, and the one side only contacted with solution can just be oxidized generation aluminum oxide film, by
It is 1cm in the internal diameter of the device washer, the oxidation film of generation is the circle of diameter 1cm.Aluminium foil after second is aoxidized is put into
It goes in the reactor of bottom, the one side of oxidation film is not upward.Successively mounting gasket and plug after aluminium foil be installed, in washer and plug
Between there is a diameter to be the cylindrical hole of 0.5cm, the volume in hole is about 1mL, and saturation copper chloride is added dropwise in hole, is occurred anti-
It answers: 2Al+3Cu2+=3Cu+2Al3+, reacted from the aluminium without oxidation film one side.The part reacted away due to aluminium flake
Diameter is less than oxidation film diameter, and oxidation film still can be attached on the aluminium flake not reacted.
Third step, the processing of AAO template metal spraying
The penetrating AAO template in two sides is put into ion sputtering instrument, using Au as target, sputtering current 10mA, vacuum degree
For 3x10-2Metal spraying 5min under conditions of Pa sputters layer of Au atom in the one side of AAO template.
4th step, Fe-Co deposit the preparation of liquid and Tb-Fe-Co deposition liquid
By frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid (H3BO3), citric acid (C6H8O7) and
Ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Fe-Co alloy/C electrolytic deposition liquid.Its molar concentration matches model
It encloses are as follows: C (FeCl2·4H2O)=0.35mol/L, C (CoCl2·6H2O)=0.15mol/L, C (H3BO3)=0.48mol/L, C
(C6H8O7)=0.06mol/L, C (C6H8O6)=0.01mol/L, the pH of obtained solution are 2.
By terbium chloride (TbCl3·6H2O), frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid
(H3BO3), glycine (C2H5NO2) and ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Tb-Fe-Co alloy electricity
Solution deposition liquid.Its molar concentration ratio range are as follows: C (TbCl3·6H2O)=0.5mol/L, C (FeCl2·4H2O)=0.1mol/
L, C (CoCl2·6H2O)=0.1mol/L, C (H3BO3)=0.48mol/L, C (C2H5NO2)=0.29mol/L, C (C6H8O6)=
0.02mol/L, the pH of obtained solution are 1.8.
5th step, the deposition of Tb-Fe-Co alloy nano-wire
AAO template after metal spraying is mounted in dislodger, using AAO template as cathode, graphite is anode, energization direct current
Pressure is 2.5V, deposition current 2mA, while uniform (revolving speed 2r/s) with magnetic stirrer solution, carries out alloy nano
The preparation of line.Fe-Co solution is poured into dislodger first, energization 15s, in the bottom deposit part Fe-Co of AAO form plate hole
Bielement nano line, is then changed to Tb-Fe-Co solution for solution, and conduction time 1.5h can be prepared by Tb-Fe-Co alloy nano
Line.
Tb-Fe-Co ternary RE alloy magnetic nanometer obtained by the present embodiment is amorphous state, and nanowire alignment has
Sequence, metallic atom ratio are Tb:Fe:Co=2:2:1, and mass ratio is about 6:2:1.
Fig. 4 is using Hitachi S-4800 type field emission scanning electron microscope to AAO template made from the embodiment of the present invention 1
FESEM figure, wherein Fig. 4 (a) and Fig. 4 (b) is respectively the front elevation and side view of AAO template.As can be seen that the AAO mould of preparation
Plate surface is smooth, and hole is uniformly and high-sequential, pore size are consistent substantially, with being averaged for Ruler software measurement hole
Diameter is 76nm, and pitch of holes is about 100nm.Nano aperture all tends to be round substantially, and the geometrical orientation difference of adjacent holes is substantially
60°。
Fig. 5 is using Hitachi S-4800 type field emission scanning electron microscope to Tb-Fe-Co made from the embodiment of the present invention 1
The FESEM map of ternary RE alloy magnetic nanometer film.Fig. 5 (a) is the front scan photo of Tb-Fe-Co nano wire, right
Upper angle is the enlarged drawing of region (1).As seen from the figure, nano wire compact arrangement, high-sequential, smooth densification, line footpath are uniform
Unanimously, average diameter 74.94nm is suitable with the internal diameter of AAO pattern hole.It is remaining since nano wire is partially to be dissociated
AAO template still plays supporting role to nano wire.Fig. 5 (b) is the side scanned photograph of Tb-Fe-Co magnetic nanometer, can be with
Find out, nano wire linear structure is obvious, vertical formwork close-packed arrays.Fig. 5 (c) is facing when nano wire dissociation degree is larger
Figure, it can be seen that the filling rate of nano wire is very high, the hole not being deposited does not occur；The bottom of nano wire due to not by
Dissociation is still in the hole of AAO template, and due to attracting each other and the cluster of reuniting that lodges, nano wire occurs curved at the top of nano wire
It is bent and do not fracture, illustrate with good elasticity.Fig. 5 (d) is the side view after a branch of nano wire will be completely dissociated, and can be seen
Out, the length uniformity of nano wire is about 23.21um.
Fig. 6 is using Hitachi S-4800 type field emission scanning electron microscope to Tb-Fe-Co made from the embodiment of the present invention 1
The EDS map of multielement rare earth alloy magnetic nanometer film.As can be seen that atomic ratio is about Tb:Fe in Tb-Fe-Co nano wire:
Co=2:2:1, mass ratio are about 6:2:1.
Fig. 7 is dilute to the more members of Tb-Fe-Co made from the embodiment of the present invention 1 using Philips PW1700 type X-ray diffractometer
The XRD spectrum of native alloy magnetic nanometer film.As can be seen that there is the steamed bun peak of apparent amorphous phase to occur in figure, illustrate Tb-
Fe-Co nano wire non crystalline structure exists.Other than steamed bun peak occur 3 crystal diffraction maximum respectively correspond FeCo phase < 100
>,<200>and<211>diffraction surfaces.On the one hand the appearance of FeCo diffraction maximum may be Tb-Fe-Co Fe, Co atom shape in deposition
At crystal；It on the other hand may be shape in the Fe-Co bielement nano line deposited before depositing Tb-Fe-Co ternary nano line
At crystal.
Fig. 8 is using 7407 type vibrating specimen magnetometer of Lake Shore Model to Fe- made from the embodiment of the present invention 1
The VSM map of the magnetic property of Co binary alloy nano line film and Tb-Fe-Co ternary RE alloy magnetic nanometer film: (a)
Fe-Co binary alloy nano line film；(b) Tb-Fe-Co ternary RE alloy magnetic nanometer film.In conjunction with the magnetism in table 1
Can data analysis it is found that Tb-Fe-Co ternary RE alloy nano-wire external magnetic field is parallel and the both direction of vertical nano-wire,
Magnetic property has very big difference, has biggish shape anisotropy；Coercivity, the saturation magnetic of Tb-Fe-Co ternary alloy nano line
Change intensity and remanent magnetism compares Fe-Co binary alloy nano line and has large increase, magnetism is able to satisfy as magnetooptical memory material
It is required that therefore Tb-Fe-Co ternary RE alloy magnetic nanometer film prepared by the present invention be suitable as a kind of Magneto-optical storages material
Material.
Table 1 is Fe-Co binary alloy nano line film and Tb-Fe-Co ternary RE alloy magnetic nanometer film in Fig. 8
Magnetic property VSM map magnetic property data.
The magnetic property data of 1 Fe-Co and Tb-Fe-Co nano wire of table
Table 2 be the element of Tb-Fe-Co multielement rare earth alloy magnetic nanometer film that EDS map show in Fig. 6 form and
Corresponding atomic ratio and mass ratio.
2 Tb-Fe-Co nano wire gamma-spectrometric data of table
Embodiment 2
The first step, aluminium flake pretreatment
By with a thickness of 0.3mm, the high-purity aluminum foil that purity is 99.999%, aluminium flake oxygen is being prevented full of argon gas or nitrogen etc.
It anneals in the protective atmosphere of change, annealing temperature: 400 DEG C of annealings, annealing time: 6h.
The pretreatment such as successively cleaned, remove surface natural oxide film, polishing treatment to the aluminium foil of annealing.
Cleaning: aluminium foil is successively put into acetone and dehydrated alcohol, the ultrasonic cleaner ultrasonic cleaning through 2000w
3min。
Removal surface natural oxide film: the aluminium foil after cleaning is immersed in 10min in the NaOH solution of 10%wt, Zhi Houyong
Deionized water is rinsed well.
Polishing treatment: using graphite as cathode, the aluminium foil of removal surface natural oxide film is anode, using DC voltage 13V
Polishing 6min is carried out in polishing fluid.Polishing fluid configuration proportion is volume ratio VDehydrated alcohol: VPerchloric acid(perchloric acid concentration is 70% to=3:1
wt)。
Second step, the preparation of anodic oxidation aluminium formwork (AAO template)
Aluminium foil is mounted in oxidation trough after pretreatment, is poured into oxalic acid solution and is carried out first time oxidation, aoxidizes for the first time
Aluminium foil afterwards will impregnate 4h in treatment fluid, be mounted in oxidation trough by the aluminium flake impregnated again later, pour into oxalic acid solution
Second is carried out to aoxidize.Oxidizing condition: the oxalic acid solution of 0.5mol/L, energization DC voltage 30V, 10 DEG C of temperature, oxidization time
4h.The treatment fluid is the H of 6%wt3PO4The H of solution and 1.8%wt2CrO3The mixed liquor of solution, wherein mass ratio is
H3PO4Solution: H2CrO3Solution=10:3.Aluminium foil after second is aoxidized is put into the reactor of bottom, not the one of oxidation film
Up, by the CuCl of saturation2Solution 0.8mL is added dropwise on aluminium foil, aluminium foil is taken out after reaction, 5% after cleaning up
The H of wt3PO460min is impregnated in solution, and the penetrating AAO template in two sides is made.
Third step, the processing of AAO template metal spraying
The penetrating AAO template in two sides is put into ion sputtering instrument, using Au as target, sputtering current 10mA, vacuum degree
For 4x10-2Metal spraying 3min under conditions of Pa sputters layer of Au atom in the one side of AAO template.
4th step, Fe-Co deposit the preparation of liquid and Tb-Fe-Co deposition liquid
By frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid (H3BO3), citric acid (C6H8O7) and
Ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Fe-Co alloy/C electrolytic deposition liquid.Its molar concentration matches model
It encloses are as follows: C (FeCl2·4H2O)=0.35mol/L, C (CoCl2·6H2O)=0.15mol/L, C (H3BO3)=0.4mol/L, C
(C6H8O7)=0.05mol/L, C (C6H8O6)=0.01mol/L, the pH of solution are 2.
By terbium chloride (TbCl3·6H2O), frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid
(H3BO3), glycine (C2H5NO2) and ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Tb-Fe-Co alloy electricity
Solution deposition liquid.Its molar concentration ratio range are as follows: C (TbCl3·6H2O)=0.4mol/L, C (FeCl2·4H2O)=0.6mol/
L, C (CoCl2·6H2O)=0.6mol/L, C (H3BO3)=0.4mol/L, C (C2H5NO2)=0.35mol/L, C (C6H8O6)=
0.02mol/L, the pH of solution are 2.5.
5th step, the deposition of Tb-Fe-Co alloy nano-wire
AAO template after metal spraying is mounted in dislodger, using AAO template as cathode, graphite is anode, energization direct current
Pressure is 2V, deposition current 0.5mA, while uniform (revolving speed 2r/s) with magnetic stirrer solution, carries out alloy nano
The preparation of line.Fe-Co solution is poured into dislodger first, energization 10s, in the bottom deposit part Fe-Co of AAO form plate hole
Bielement nano line, is then changed to Tb-Fe-Co solution for solution, and conduction time 1h can be prepared by Tb-Fe-Co alloy nano-wire.
Tb-Fe-Co ternary RE alloy magnetic nanometer obtained by the present embodiment is amorphous state, and nanowire alignment has
Sequence, metallic atom ratio are Tb:Fe:Co=1:2:2, and mass ratio is about 6:2:1.
Embodiment 3
The first step, aluminium flake pretreatment
By with a thickness of 0.3mm, the high-purity aluminum foil that purity is 99.999%, aluminium flake oxygen is being prevented full of argon gas or nitrogen etc.
It anneals in the protective atmosphere of change, annealing temperature: 500 DEG C of annealings, annealing time: 5h.
The pretreatment such as successively cleaned, remove surface natural oxide film, polishing treatment to the aluminium foil of annealing.
Cleaning: aluminium foil is successively put into acetone and dehydrated alcohol, the ultrasonic cleaner ultrasonic cleaning through 1000w
7min。
Removal surface natural oxide film: the aluminium foil after cleaning is immersed in 30min in the NaOH solution of 5%wt, Zhi Houyong
Deionized water is rinsed well.
Polishing treatment: using graphite as cathode, the aluminium foil of removal surface natural oxide film is anode, using DC voltage 18V
Polishing 3min is carried out in polishing fluid.Polishing fluid configuration proportion is volume ratio VDehydrated alcohol: VPerchloric acid(perchloric acid concentration is 70% to=3:1
wt)。
Second step, the preparation of anodic oxidation aluminium formwork (AAO template)
Aluminium foil is mounted in oxidation trough after pretreatment, is poured into oxalic acid solution and is carried out first time oxidation, aoxidizes for the first time
Aluminium foil afterwards will impregnate 4h in treatment fluid, be mounted in oxidation trough by the aluminium flake impregnated again later, pour into oxalic acid solution
Second is carried out to aoxidize.Oxidizing condition: the oxalic acid solution of 0.3mol/L, energization DC voltage 50V, 0 DEG C of temperature, oxidization time
5h.The treatment fluid is the H of 6%wt3PO4The H of solution and 1.8%wt2CrO3The mixed liquor of solution, wherein mass ratio is
H3PO4Solution: H2CrO3Solution=10:5.Aluminium foil after second is aoxidized is put into the reactor of bottom, not the one of oxidation film
Up, by the CuCl of saturation2Solution 0.8mL is added dropwise on aluminium foil, aluminium foil is taken out after reaction, 5% after cleaning up
The H of wt3PO450min is impregnated in solution, and the penetrating AAO template in two sides is made.
Third step, the processing of AAO template metal spraying
The penetrating AAO template in two sides is put into ion sputtering instrument, using Au as target, sputtering current 12mA, vacuum degree
For 6x10-2Metal spraying 4min under conditions of Pa sputters layer of Au atom in the one side of AAO template.
4th step, Fe-Co deposit the preparation of liquid and Tb-Fe-Co deposition liquid
By frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid (H3BO3), citric acid (C6H8O7) and
Ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Fe-Co alloy/C electrolytic deposition liquid.Its molar concentration matches model
It encloses are as follows: C (FeCl2·4H2O)=0.4mol/L, C (CoCl2·6H2O)=0.4mol/L, C (H3BO3)=0.5mol/L, C
(C6H8O7)=0.08mol/L, C (C6H8O6)=0.02mol/L.Wherein citric acid plays complexing agent and adjusts pH value, molten
The pH of liquid is 3.
By terbium chloride (TbCl3·6H2O), frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid
(H3BO3), glycine (C2H5NO2) and ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Tb-Fe-Co alloy electricity
Solution deposition liquid.Its molar concentration ratio range are as follows: C (TbCl3·6H2O)=0.6mol/L, C (FeCl2·4H2O)=
0.15mol/L, C (CoCl2·6H2O)=0.15mol/L, C (H3BO3)=0.6mol/L, C (C2H5NO2)=0.35mol/L, C
(C6H8O6)=0.01mol/L, the pH of solution are 2.5.
5th step, the deposition of Tb-Fe-Co alloy nano-wire
In the reactor by the AAO template installation after metal spraying, using AAO template as cathode, graphite is anode, energization direct current
Pressure is 3V, deposition current 3mA, while uniform (revolving speed 3r/s) with magnetic stirrer solution, carries out alloy nano-wire
Preparation.Fe-Co solution is poured into dislodger first, energization 10s, in the bottom deposit part Fe-Co bis- of AAO form plate hole
First nano wire, is then changed to Tb-Fe-Co solution for solution, and conduction time 0.5h can be prepared by Tb-Fe-Co alloy nano-wire.
Tb-Fe-Co ternary RE alloy magnetic nanometer obtained by the present embodiment is amorphous state, and nanowire alignment has
Sequence, metallic atom ratio are Tb:Fe:Co=3:1:1, and mass ratio is about 8:2:1.
Embodiment 4
The first step, aluminium flake pretreatment
By with a thickness of 0.3mm, the high-purity aluminum foil that purity is 99.999%, aluminium flake oxygen is being prevented full of argon gas or nitrogen etc.
It anneals in the protective atmosphere of change, annealing temperature: 450 DEG C of annealings, annealing time: 4h.
The pretreatment such as successively cleaned, remove surface natural oxide film, polishing treatment to the aluminium foil of annealing.
Cleaning: aluminium foil is successively put into acetone and dehydrated alcohol, and the ultrasonic cleaner through 800w is cleaned by ultrasonic 8min.
Removal surface natural oxide film: the aluminium foil after cleaning is immersed in 30min in the NaOH solution of 5%wt, Zhi Houyong
Deionized water is rinsed well.
Polishing treatment: using graphite as cathode, the aluminium foil of removal surface natural oxide film is anode, using DC voltage 16V
Polishing 4min is carried out in polishing fluid.Polishing fluid configuration proportion is volume ratio VDehydrated alcohol: VPerchloric acid(perchloric acid concentration is 70% to=5:1
wt)。
Second step, the preparation of anodic oxidation aluminium formwork (AAO template)
Aluminium foil is mounted in oxidation trough after pretreatment, is poured into oxalic acid solution and is carried out first time oxidation, aoxidizes for the first time
Aluminium foil afterwards will impregnate 4h in treatment fluid, be mounted in oxidation trough by the aluminium flake impregnated again later, pour into oxalic acid solution
Second is carried out to aoxidize.Oxidizing condition: the oxalic acid solution of 0.4mol/L, energization DC voltage 45V, 5 DEG C of temperature, oxidization time
7h.The treatment fluid is the H of 6%wt3PO4The H of solution and 1.8%wt2CrO3The mixed liquor of solution, wherein mass ratio is
H3PO4Solution: H2CrO3Solution=10:4.Aluminium foil after second is aoxidized is put into the reactor of bottom, not the one of oxidation film
Up, by the CuCl of saturation2Solution 0.8mL is added dropwise on aluminium foil, aluminium foil is taken out after reaction, 10% after cleaning up
The H of wt3PO440min is impregnated in solution, and the penetrating AAO template in two sides is made.
Third step, the processing of AAO template metal spraying
The penetrating AAO template in two sides is put into ion sputtering instrument, using Au as target, sputtering current 10mA, vacuum degree
For 3x10-2Metal spraying 6min under conditions of Pa sputters layer of Au atom in the one side of AAO template.
4th step, Fe-Co deposit the preparation of liquid and Tb-Fe-Co deposition liquid
By frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid (H3BO3), citric acid (C6H8O7) and
Ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Fe-Co alloy/C electrolytic deposition liquid.Its molar concentration matches model
It encloses are as follows: C (FeCl2·4H2O)=0.55mol/L, C (CoCl2·6H2O)=0.35mol/L, C (H3BO3)=0.4mol/L, C
(C6H8O7)=0.09mol/L, C (C6H8O6)=0.01mol/L.Wherein citric acid plays complexing agent and adjusts pH value, molten
The pH of liquid is 3.5.
By terbium chloride (TbCl3·6H2O), frerrous chloride (FeCl2·4H2O), cobalt chloride (CoCl2·6H2O), boric acid
(H3BO3), glycine (C2H5NO2) and ascorbic acid (C6H8O6) be add to deionized water, preparation obtains Tb-Fe-Co alloy electricity
Solution deposition liquid.Its molar concentration ratio range are as follows: C (TbCl3·6H2O)=0.8mol/L, C (FeCl2·4H2O)=
0.15mol/L, C (CoCl2·6H2O)=0.15mol/L, C (H3BO3)=0.5mol/L, C (C2H5NO2)=0.3mol/L, C
(C6H8O6)=0.03mol/L, the pH of solution are 2.6.
5th step, the deposition of Tb-Fe-Co alloy nano-wire
AAO template after metal spraying is mounted in dislodger, using AAO template as cathode, graphite is anode, energization direct current
Pressure is 2.7V, deposition current 2.5mA, while uniform (revolving speed 1r/s) with magnetic stirrer solution, carries out alloy and receives
The preparation of rice noodles.Fe-Co solution is poured into dislodger first, energization 60s, in the bottom deposit part Fe- of AAO form plate hole
Co bielement nano line, is then changed to Tb-Fe-Co solution for solution, and conduction time 0.5h can be prepared by Tb-Fe-Co alloy nano
Line.
Tb-Fe-Co ternary RE alloy magnetic nanometer obtained by the present embodiment is amorphous state, and nanowire alignment has
Sequence, metallic atom ratio are Tb:Fe:Co=3:2:1, and mass ratio is about 9:4:1.
In above-mentioned all embodiments material therefor from market buy gained, equipment oxidation trough used, go bottom reactor,
Ion sputtering instrument and dislodger are well known preparation AAO template and electrochemical deposition nano wire stand-by equipment.
Unaccomplished matter of the present invention is well-known technique.
Claims (2)
1. a kind of preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film, it is characterized in that this method includes following
Step:
The first step, the processing of AAO template metal spraying
AAO template is put into ion sputtering instrument, using Au as target, sputtering current 10mA, vacuum degree 3x10-2The condition of Pa
Lower metal spraying 5min~10min sputters layer of Au atom in the one side of AAO template, and Au atomic layer level thickness is 1 μm~10 μm；
Second step, Fe-Co deposit the preparation of liquid and Tb-Fe-Co deposition liquid
By frerrous chloride, cobalt chloride, boric acid (H3BO3), citric acid (C6H8O7) and ascorbic acid (C6H8O6) it is added to deionized water
In, preparation obtains Fe-Co alloy/C electrolytic deposition liquid；Deposit the concentration of each material in liquid are as follows: C (frerrous chloride)=0.35mol/L
~0.55mol/L, C (cobalt chloride)=0.15mol/L~0.35mol/L, C (H3BO3)=0.4mol/L~0.6mol/L, C
(C6H8O7)=0.05mol/L~0.09mol/L, C (C6H8O6)=0.01mol/L~0.03mol/L；
By terbium chloride, frerrous chloride, cobalt chloride, boric acid (H3BO3), glycine (C2H5NO2) and ascorbic acid (C6H8O6) be added to
In deionized water, preparation obtains Tb-Fe-Co alloy electrolytic deposition liquid；Deposit the concentration of each material in liquid are as follows: C (terbium chloride)=
0.4mol/L~1mol/L, C (frerrous chloride)=0.1mol/L~1mol/L, C (cobalt chloride)=0.1mol/L~1mol/L, C
(H3BO3)=0.4mol/L~0.6mol/L, C (C2H5NO2)=0.25mol/L~0.65mol/L, C (C6H8O6)=0.01mol/
L~0.03mol/L；
Third step, the deposition of Tb-Fe-Co multielement rare earth alloy magnetic nanometer
AAO template is mounted in dislodger, is first poured into Fe-Co alloy/C electrolytic deposition liquid in dislodger, is with AAO template
Cathode, graphite are anode, and energization DC voltage is 2V~3V, and deposition current is 0.5mA~20mA, while being stirred with magnetic stirring apparatus
Mix solution；Then energization 10s~60s closes Fe-Co in the bottom deposit part Fe-Co bielement nano line of AAO form plate hole
Gold electrolysis deposition liquid is poured out, then pours into Tb-Fe-Co alloy electrolytic deposition liquid, and conduction time 0.5h~12h can be prepared by Tb-
Fe-Co alloy/C nano wire.
2. the preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film as described in claim 1, it is characterized in that
Magnetic agitation rotating speed is 1r/s~5r/s in the third step.
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| CN1485466A (en) * | 2002-09-27 | 2004-03-31 | 长沙高新技术产业开发区英才科技有限 | Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material |
| CN101509142A (en) * | 2009-03-31 | 2009-08-19 | 哈尔滨工业大学 | Method for producing TbFeCo alloy film by using ionic liquid impulse electrodeposition technology |
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| CN101509142A (en) * | 2009-03-31 | 2009-08-19 | 哈尔滨工业大学 | Method for producing TbFeCo alloy film by using ionic liquid impulse electrodeposition technology |
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| Title |
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| "Fabrication of Rare Earth-Transition Metal Alloy Nanowires and Nanotubes";R.Mishra et al.;《ECS Transactions》;20060731;第1卷(第23期);第9-16页 |
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