CN108277462A - A kind of method that pulse electrodeposition prepares magnetic metal nanotube - Google Patents
A kind of method that pulse electrodeposition prepares magnetic metal nanotube Download PDFInfo
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- CN108277462A CN108277462A CN201711451598.6A CN201711451598A CN108277462A CN 108277462 A CN108277462 A CN 108277462A CN 201711451598 A CN201711451598 A CN 201711451598A CN 108277462 A CN108277462 A CN 108277462A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0005—Separation of the coating from the substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
Abstract
The present invention relates to a kind of to have the method that the pulse electrodeposition of huge potential application foreground prepares magnetic metal nanotube in terms of magnetic pipe recording material, the method has the advantages that simple and convenient, operability is extremely strong, effectively the length and diameter of prepared magnetic metal nanotube can be controlled, and this method cost is relatively low, required accuracy of instrument requires not harsh, applicability is extremely strong, a variety of magnetic metal nanotubes can be prepared, it is not limited to prepare single magnetic metal nanotube, and processing step is not substantially change, and is conducive to mass production preparation.
Description
Technical field
The present invention relates to a kind of fields of metal nano tube preparation method, more particularly to one kind is in terms of magnetic pipe recording material
The method that pulse electrodeposition with huge potential application foreground prepares magnetic metal nanotube.
Background technology
Currently, the synthetic method of magnetic metal nanotube mainly has chemical plating, atomic layer deposition（ALD）, sol-gel
（sol-gel）With electro-deposition etc..Wherein chemical plating can only prepare the higher metal that can be restored by chemical reagent of reduction potential, such as
Ni, Co etc.；ALD needs accurate instrument and is only suitable for preparing Fe3O4Equal oxides；Sol-gel methods are although simple and convenient, are not required to
Any precision instrument is wanted, but equally can only also prepare oxide.In addition, the above method can not pass through the length of control nanotube
The performance of nanotube is adjusted with diameter.
Therefore, template assisted electrochemical is deposited on prepare metal magnetic nano-tube array in terms of there is big advantage, can
Easily to control the ingredient and structure of nanotube, operability is strong, simple and convenient.So far, there are a series of metals
Nano-tube array is made by the method for traditional electrochemical deposition, but on the one hand requires relatively high, another party to conductive layer
Face can introduce the performance that impurity seriously affects material.
Patent Office of the People's Republic of China disclosed on June 13rd, 2017 a kind of preparing metal nanoparticle/graphene/carbon nano-tube material
The invention patent mandate of the method for material, Authorization Notice No. CN105251979B, the patent of invention provide a kind of that metal salt is molten
Liquid, graphite oxide and carbon nanotube are dispersed in water, ethyl alcohol, n,N-Dimethylformamide lamp solvent and are irradiated, and preparation is provided
The process for having metal nanoparticle/graphene/carbon nano tube nanocomposite material of low infrared emissivity, can prepare
Composite nano-tube material with certain property, but its exist as conventional method can not to the length of nanotube and directly
Diameter is controlled, can not to prepare high-quality magnetic metal nanotube carry out prepare and cost is excessively high and single method can only be prepared
The problems such as particular types nanotube.
Invention content
It, can not be to preparing high-quality magnetic gold to solve in the prior art not controlling the length and diameter of nanotube
The problems such as category nanotube prepare and cost is excessively high and single method can only prepare particular types nanotube, provides one kind
Magnetic can be prepared to the pulse electrodeposition that nanotube length and diameter are controlled, cost is relatively low, simple for process, applied widely
The method of property metal nano-tube.
To achieve the above object, the present invention uses following technical scheme：
A kind of method that pulse electrodeposition prepares magnetic metal nanotube, the pulse electrodeposition prepare magnetic metal nanotube
Method includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Annealing will be passed through, the pretreated aluminium flake of supersound washing is placed in 0.3~0.5mol/L oxalic acid aqueous solutions
In, 4~6h of electrochemical corrosion under the conditions of 40~60V of voltage, 0~3 DEG C of temperature obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained is placed in 50~70 DEG C of phosphoric acid and chromium
12~16h is impregnated in sour mixed aqueous solution, is cleaned up later with deionized water, and the aluminium flake of removal once oxidation film is obtained；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.3~0.5mol/L oxalic acid
In aqueous solution, 6~8h of electrochemical corrosion under the conditions of 80~90V of voltage, 0~3 DEG C of temperature, taking-up is cleaned with deionized water, then
It is placed in 1~3mol/LCuCl210~60min is impregnated in aqueous solution, is cleaned up later with deionized water, is obtained receiving containing bilateral
The alumina formwork of metre hole；
（a-4）Reaming：At 30~35 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 3~
5wt%H3PO420~45min of reaming in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 10~30sccm, and air pressure is 3~5 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 150~200Pa；
（b-2）Pulse electrodeposition：Three-electrode system is built, with step（b-1）The anodic oxidation aluminium formwork of obtained sputtering copper film
As working electrode, platinized platinum be to electrode, saturated calomel electrode it is auxiliary electrode, auxiliary electrode is immersed in saturation KCl solution
In, electrode and working electrode are impregnated in the electrolytic solution, saturation KCl solution is connected with salt bridge and electrolyte carries out electro-deposition, sink
Product potential is square-wave pulse potential, deposits 10~15s in 0V first, then add -3V 1~3s of potential deposition, is recycled as one,
Deposition process carries out 164~492 cycles in total；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition, which is soaked in alkaline solution, removes alumina formwork and copper film,
Up to the magnetic metal nanotube.
Preferably, step（a-1）Described in annealing aluminum sheet, supersound washing pretreatment be：Aluminium flake is first placed in 500 DEG C
Under the conditions of anneal 2~4h, then ultrasound 10min in acetone, then 5~10min of immersion in alkaline solution, finally in acetone
Middle ultrasonic 3~5min, the aluminium flake are the thin slice of 50~60 μ m thicks.
Preferably, alkaline solution described in pretreatment is the sodium hydrate aqueous solution of 5wt%.
Preferably, step（a-2）Described in phosphoric acid and chromic acid mixed aqueous solution phosphoric acid concentration be 3~6wt%, chromic acid
A concentration of 1~2wt%.
Preferably, step（b-2）Described in contain the raw materials of following parts by weight in salt bridge：0.95~1.0 part of agar,
8~12 parts of potassium chloride, 25~35 parts of deionized water.
Preferably, step（b-2）The electrolyte includes but not limited to：Nickel salt solution, cobalt salt solution and ferrous salt
Solution.
Preferably, the nickel salt solution is dissolved with 300~400g/L NiSO4•6H2O, 45~60g/L NiCl2•6H2O
With 45~60g/L H3BO3Aqueous solution, nickel salt solution pH value be 3~5.
Preferably, the cobalt salt solution is dissolved with 300~400 g/L CoSO4•6H2O, 45~60 g/L CoCl2•
6H2O and 45~60 g/L H3BO3Aqueous solution, cobalt salt solution pH value be 3~5.
Preferably, the ferrous salt solution is dissolved with 300~400 g/L FeSO4•6H2O, 45~60 g/L FeCl2•
6H2O, 15~30 g/L ascorbic acid and 45~60 g/L H3BO3Aqueous solution, ferrous salt solution pH value be 3~5.
Preferably, step（c）Described in alkaline solution be 5wt% sodium hydrate aqueous solutions, soaking time be 0.5~2h.
Pulse electrodeposition has been developed in recent years a kind of novel electroplating technology, utilizes of current or voltage pulse
The activation polarization of cathode can be increased and reduce the concentration difference variation of cathode by relaxing, and improve the purity, density and the uniformity of sedimentary, and
Reduce the voidage of its sedimentary, improve sedimentary quality, compared to the prior art in common electro-deposition, the nanometer prepared
Pipe purity more high-voidage is less, improves the quality of nanotube.
To basic masterplate using the primary removal of oxidation twice, and it is subject to the technique of reaming, has been prepared to follow-up arteries and veins
It rushes electro-deposition and prepares magnetic metal nanotube and provide a kind of extremely good anode masterplate, for the follow-up magnetism for preparing high quality
Metal nano-tube provides advantageous prerequisite.
Sputtering copper film provides conductive layer, and facilitates removal, greatly reduces miscellaneous in prepared Magnetic nano-pipe
Matter content, can the opposite performance for improving obtained magnetic metal nano-tube material.
Three-electrode system provides an electro-deposition environment that is complete, stablizing, is subject to the mode of pulse electrodeposition, greatly
Purity, density and the uniformity of preparation-obtained magnetic metal sedimentary are improved, and reduces the sky of its magnetic metal sedimentary
Gap rate improves magnetic metal sedimentary quality.
The beneficial effects of the invention are as follows：
1）The method that pulse electrodeposition provided by the present invention prepares magnetic metal nanotube has simple and convenient, operability pole
Strong advantage；
2）Method provided by the present invention can effectively control the length and diameter of prepared magnetic metal nanotube；
3）Method cost provided by the present invention is relatively low, and required accuracy of instrument requirement is not harsh, and applicability is extremely strong；
4）Method provided by the present invention can be prepared a variety of magnetic metal nanotubes, be not limited to prepare single magnetism gold
Belong to nanotube, and processing step is not substantially change, is conducive to mass production preparation.
Description of the drawings
Fig. 1 is the device of the invention schematic diagram；
Fig. 2 is the formation schematic diagram of nanotube；
One cycle added square wave current potential schematic diagram when Fig. 3 is pulse electrodeposition；
Fig. 4 is the scanning electron microscopic picture of the template surface prepared by the present invention；
Fig. 5 is the scanning electron microscopic picture of the template cross section prepared by the present invention；
Fig. 6 is the projection electron microscopic picture of the magnetic metal Ni nanotubes prepared by the present invention；
In figure, 1 saturated calomel electrode, 2 platinum plate electrodes, the anodic oxidation aluminium formwork of 3 sputtering copper films, 4 salt bridges, 5 electrochemical operations
It stands.
Specific implementation mode
It is carried out with reference to the embodiment of the present invention and Figure of description technical solution in the embodiment of the present invention clear, complete
Site preparation describes, it is clear that described embodiment is only a part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
Belong to protection scope of the present invention.
According to Fig. 1 construction devices, as described in Figure 1
Embodiment 1
A kind of method that pulse electrodeposition prepares magnetic metal nanotube, the pulse electrodeposition prepare magnetic metal nanotube
Method includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Aluminium flake is placed under the conditions of 500 DEG C the 4h that anneals, then ultrasound 10min in acetone, then existed
5min is impregnated in the sodium hydrate aqueous solution of 5wt%, in acetone ultrasound 3min, then will pass through pretreatment aluminium flake and be placed in 0.3mol/
In L oxalic acid aqueous solutions, electrochemical corrosion 4h under the conditions of voltage 40V, 0 DEG C of temperature obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained, the phosphoric acid concentration for being placed in 65 DEG C are
12h is impregnated in the phosphoric acid and chromic acid mixed aqueous solution of 6wt% and a concentration of 1.5wt% of chromic acid, is cleaned up later with deionized water,
Obtain the aluminium flake of removal once oxidation film；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.3mol/L oxalic acid aqueous solutions
In, electrochemical corrosion 8h under the conditions of voltage 80V, 0 DEG C of temperature, taking-up is cleaned with deionized water, then is placed in 1mol/LCuCl2Water
30min is impregnated in solution, is cleaned up later with deionized water, and the alumina formwork containing bi-pass nano hole is obtained；
（a-4）Reaming：At 35 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 5wt%
H3PO4Reaming 45min in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 20sccm, and air pressure is 4 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 175Pa；
（b-2）Pulse electrodeposition：Three-electrode system is built, with step（b-1）The anodic oxidation aluminium formwork of obtained sputtering copper film
As working electrode, platinized platinum be to electrode, saturated calomel electrode it is auxiliary electrode, auxiliary electrode is immersed in saturation KCl solution
In, electrode and working electrode are impregnated in the electrolytic solution, saturation KCl solution is connected with salt bridge and electrolyte carries out electro-deposition, sink
Product potential is square-wave pulse potential, deposits 10s in 0V first, then add -3V potential deposition 1s, recycles, deposited as one
Journey carries out 328 cycles in total, and one of added square wave current potential of cycle is as shown in Figure 3；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition is soaked in 5wt% sodium hydrate aqueous solutions, and soaking time is
1.5h removes alumina formwork and copper film to get the magnetic metal nanotube.
The aluminium flake thin slice of 50 μ m thicks is selected in the present embodiment；In salt bridge used contain 1.0 parts of agar, 10 parts of potassium chloride,
The raw material that 29 parts of deionized water；The present embodiment step（b-2）Used in electrolyte be 300g/L NiSO4•6H2O、45g/L
NiCl2•6H2O and 45g/L H3BO3Nickel salt solution, pH value 3；Obtained magnetic metal nanotube is that magnetic metal Ni receives
Mitron.
Embodiment 2
A kind of method that pulse electrodeposition prepares magnetic metal nanotube, the pulse electrodeposition prepare magnetic metal nanotube
Method includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Aluminium flake is placed under the conditions of 500 DEG C the 4h that anneals, then ultrasound 10min in acetone, then existed
5min is impregnated in the sodium hydrate aqueous solution of 5wt%, in acetone ultrasound 3min, then will pass through pretreatment aluminium flake and be placed in 0.3mol/
In L oxalic acid aqueous solutions, electrochemical corrosion 4h under the conditions of voltage 40V, 0 DEG C of temperature obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained, the phosphoric acid concentration for being placed in 65 DEG C are
12h is impregnated in the phosphoric acid and chromic acid mixed aqueous solution of 6wt% and a concentration of 1.5wt% of chromic acid, is cleaned up later with deionized water,
Obtain the aluminium flake of removal once oxidation film；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.5mol/L oxalic acid aqueous solutions
In, electrochemical corrosion 8h under the conditions of voltage 80V, 0 DEG C of temperature, taking-up is cleaned with deionized water, then is placed in 1mol/LCuCl2Water
30min is impregnated in solution, is cleaned up later with deionized water, and the alumina formwork containing bi-pass nano hole is obtained；
（a-4）Reaming：At 35 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 5wt%
H3PO4Reaming 45min in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 10sccm, and air pressure is 3 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 150Pa；
（b-2）Pulse electrodeposition：Three-electrode system is built, with step（b-1）The anodic oxidation aluminium formwork of obtained sputtering copper film
As working electrode, platinized platinum be to electrode, saturated calomel electrode it is auxiliary electrode, auxiliary electrode is immersed in saturation KCl solution
In, electrode and working electrode are impregnated in the electrolytic solution, saturation KCl solution is connected with salt bridge and electrolyte carries out electro-deposition, sink
Product potential is square-wave pulse potential, deposits 10s in 0V first, then add -3V potential deposition 1s, recycles, deposited as one
Journey carries out 328 cycles in total, and one of added square wave current potential of cycle is as shown in Figure 3；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition is soaked in 5wt% sodium hydrate aqueous solutions, and soaking time is
1.5h removes alumina formwork and copper film to get the magnetic metal nanotube.
The aluminium flake thin slice of 60 μ m thicks is selected in the present embodiment；In salt bridge used contain 1.0 parts of agar, 10 parts of potassium chloride,
The raw material that 29 parts of deionized water；The present embodiment step（b-2）Used in electrolyte be 300 g/L FeSO4•6H2O、45 g/L
FeCl2•6H2O、45g/L H3BO3With the ferrous salt solution of 15g/L ascorbic acid, pH value 3；Obtained magnetic metal nanometer
Pipe is magnetic metal Fe nanotubes.
Embodiment 3
A kind of method that pulse electrodeposition prepares magnetic metal nanotube, the pulse electrodeposition prepare magnetic metal nanotube
Method includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Aluminium flake is placed under the conditions of 500 DEG C the 4h that anneals, then ultrasound 10min in acetone, then existed
5min is impregnated in the sodium hydrate aqueous solution of 5wt%, in acetone ultrasound 3min, then will pass through pretreatment aluminium flake and be placed in 0.3mol/
In L oxalic acid aqueous solutions, electrochemical corrosion 4h under the conditions of voltage 40V, 0 DEG C of temperature obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained, the phosphoric acid concentration for being placed in 65 DEG C are
12h is impregnated in the phosphoric acid and chromic acid mixed aqueous solution of 6wt% and a concentration of 1.5wt% of chromic acid, is cleaned up later with deionized water,
Obtain the aluminium flake of removal once oxidation film；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.5mol/L oxalic acid aqueous solutions
In, electrochemical corrosion 8h under the conditions of voltage 80V, 0 DEG C of temperature, taking-up is cleaned with deionized water, then is placed in 1mol/LCuCl2Water
30min is impregnated in solution, is cleaned up later with deionized water, and the alumina formwork containing bi-pass nano hole is obtained；
（a-4）Reaming：At 35 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 5wt%
H3PO4Reaming 45min in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 30sccm, and air pressure is 5 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 200Pa；
（b-2）Pulse electrodeposition：Three-electrode system is built, with step（b-1）The anodic oxidation aluminium formwork of obtained sputtering copper film
As working electrode, platinized platinum be to electrode, saturated calomel electrode it is auxiliary electrode, auxiliary electrode is immersed in saturation KCl solution
In, electrode and working electrode are impregnated in the electrolytic solution, saturation KCl solution is connected with salt bridge and electrolyte carries out electro-deposition, sink
Product potential is square-wave pulse potential, deposits 10s in 0V first, then add -3V potential deposition 1s, recycles, deposited as one
Journey carries out 328 cycles in total, and one of added square wave current potential of cycle is as shown in Figure 3；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition is soaked in 5wt% sodium hydrate aqueous solutions, and soaking time is
1.5h removes alumina formwork and copper film to get the magnetic metal nanotube.
The aluminium flake thin slice of 60 μ m thicks is selected in the present embodiment；In salt bridge used contain 1.0 parts of agar, 10 parts of potassium chloride,
The raw material that 29 parts of deionized water；The present embodiment step（b-2）Used in electrolyte be 300 g/L CoSO4•6H2O、45 g/L
CoCl2•6H2O and 45g/L H3BO3Cobalt salt solution, pH value 3；Obtained magnetic metal nanotube is that magnetic metal Co receives
Mitron.
Embodiment 4
A kind of method that pulse electrodeposition prepares magnetic metal nanotube, the pulse electrodeposition prepare magnetic metal nanotube
Method includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Aluminium flake is placed under the conditions of 500 DEG C the 2h that anneals, then ultrasound 10min in acetone, then existed
5min is impregnated in the sodium hydrate aqueous solution of 5wt%, in acetone ultrasound 3min, then will pass through pretreatment aluminium flake and be placed in 0.3mol/
In L oxalic acid aqueous solutions, electrochemical corrosion 4h under the conditions of voltage 40V, 0 DEG C of temperature obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained, the phosphoric acid concentration for being placed in 50 DEG C are
12h is impregnated in the phosphoric acid and chromic acid mixed aqueous solution of 3wt% and a concentration of 1wt% of chromic acid, is cleaned up, is obtained with deionized water later
To the aluminium flake of removal once oxidation film；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.3mol/L oxalic acid aqueous solutions
In, electrochemical corrosion 6h under the conditions of voltage 80V, 0 DEG C of temperature, taking-up is cleaned with deionized water, then is placed in 1mol/LCuCl2Water
10min is impregnated in solution, is cleaned up later with deionized water, and the alumina formwork containing bi-pass nano hole is obtained；
（a-4）Reaming：At 30 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 3wt%H3PO4
Reaming 20min in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 10sccm, and air pressure is 3 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 150Pa；
（b-2）Pulse electrodeposition：Three-electrode system is built, with step（b-1）The anodic oxidation aluminium formwork of obtained sputtering copper film
As working electrode, platinized platinum be to electrode, saturated calomel electrode it is auxiliary electrode, auxiliary electrode is immersed in saturation KCl solution
In, electrode and working electrode are impregnated in the electrolytic solution, saturation KCl solution is connected with salt bridge and electrolyte carries out electro-deposition, sink
Product potential is square-wave pulse potential, deposits 10s in 0V first, then add -3V potential deposition 1s, recycles, deposited as one
Journey carries out 164 cycles in total；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition is soaked in 5wt% sodium hydrate aqueous solutions, and soaking time is
0.5h removes alumina formwork and copper film to get the magnetic metal nanotube.
The aluminium flake thin slice of 50 μ m thicks is selected in the present embodiment；In salt bridge used contain 0.95 part of agar, 8 parts of potassium chloride,
The raw material that 25 parts of deionized water；The present embodiment step（b-2）Used in electrolyte be 400g/L NiSO4•6H2O、60g/L
NiCl2•6H2O and 60g/L H3BO3Nickel salt solution, pH value 5；Obtained magnetic metal nanotube is that magnetic metal Ni receives
Mitron.
Embodiment 5
A kind of method that pulse electrodeposition prepares magnetic metal nanotube, the pulse electrodeposition prepare magnetic metal nanotube
Method includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Aluminium flake is placed under the conditions of 500 DEG C the 4h that anneals, then ultrasound 10min in acetone, then existed
10min is impregnated in the sodium hydrate aqueous solution of 5wt%, in acetone ultrasound 5min, then will pass through pretreatment aluminium flake and be placed in
In 0.5mol/L oxalic acid aqueous solutions, electrochemical corrosion 6h under the conditions of voltage 60V, 3 DEG C of temperature obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained, the phosphoric acid concentration for being placed in 70 DEG C are
16h is impregnated in the phosphoric acid and chromic acid mixed aqueous solution of 6wt% and a concentration of 2wt% of chromic acid, is cleaned up, is obtained with deionized water later
To the aluminium flake of removal once oxidation film；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.5mol/L oxalic acid aqueous solutions
In, electrochemical corrosion 8h under the conditions of voltage 90V, 3 DEG C of temperature, taking-up is cleaned with deionized water, then is placed in 3mol/LCuCl2Water
60min is impregnated in solution, is cleaned up later with deionized water, and the alumina formwork containing bi-pass nano hole is obtained；
（a-4）Reaming：At 35 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 5wt%
H3PO4Reaming 45min in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 30sccm, and air pressure is 5 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 200Pa；
（b-2）Pulse electrodeposition：Three-electrode system is built, with step（b-1）The anodic oxidation aluminium formwork of obtained sputtering copper film
As working electrode, platinized platinum be to electrode, saturated calomel electrode it is auxiliary electrode, auxiliary electrode is immersed in saturation KCl solution
In, electrode and working electrode are impregnated in the electrolytic solution, saturation KCl solution is connected with salt bridge and electrolyte carries out electro-deposition, sink
Product potential is square-wave pulse potential, deposits 15s in 0V first, then add -3V potential deposition 3s, recycles, deposited as one
Journey carries out 492 cycles in total；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition is soaked in 5wt% sodium hydrate aqueous solutions, and soaking time is
2h removes alumina formwork and copper film to get the magnetic metal nanotube.
The aluminium flake thin slice of 60 μ m thicks is selected in the present embodiment；In salt bridge used contain 1.0 parts of agar, 12 parts of potassium chloride,
The raw material that 35 parts of deionized water；The present embodiment step（b-2）Used in electrolyte be 400 g/L FeSO4•6H2O、60 g/L
FeCl2•6H2O, 30 g/L ascorbic acid and 60 g/L H3BO3Ferrous salt solution, pH value 5；Obtained magnetic metal is received
Mitron is magnetic metal Fe nanotubes.
Comparative example
High-purity Al is deposited in n-type silicon substrate, PAA/Si perforated membranes are then obtained by anodic oxidation, as template in electricity
Position synthesizes the Ni nanotubes of high fill-ratio when relatively negative.
Mechanism study shows that this electro-deposition is realized by the electrical breakdown to template, and current potential is more negative, the lotus of hole wall
Electricity is higher, causes electro-deposition preferentially to be carried out in hole wall, some template apertures are closed before duct is filled up completely, it is ensured that pipe
The formation of shape structure.
Comparative example institute's application method is using Al as conductive substrates, and electric conductivity is without Cu high, therefore nanotube deposition rate is not high enough；
Secondly, the bad control of point of the method, it is difficult to operate, and the excessively negative then easy breakdown template of point, cause the damage of template.
Relatively existing nanotube deposition method, the present invention is easy to operate, and point controls well, is not influenced on template, together
When, Cu base conductives are good, and the deposition of nanotube is high, to used in embodiment 1 template surface and cross section be scanned electricity
Microscopy is surveyed and is scanned Electronic Speculum detection to the magnetic metal Ni nanotubes obtained by embodiment 1, and it is template that the results are shown in Figure 4
The surface sweeping electron microscopic picture on surface, is illustrated in figure 5 the scanning electron microscopic picture of template cross section, and it is made to be illustrated in figure 6 embodiment 1
The scanning electron microscopic picture of the magnetic metal Ni nanotubes obtained.
Claims (10)
1. a kind of method that pulse electrodeposition prepares magnetic metal nanotube, which is characterized in that the pulse electrodeposition prepares magnetic
The method of property metal nano-tube includes the following steps：
（a）It is prepared by template
（a-1）Once oxidation：Annealing will be passed through, the pretreated aluminium flake of supersound washing is placed in 0.3~0.5mol/L oxalic acid aqueous solutions
In, 4~6h of electrochemical corrosion obtains once oxidation aluminium flake；
（a-2）Remove once oxidation film：Take step（a-1）Once oxidation aluminium flake obtained is placed in 50~70 DEG C of phosphoric acid and chromium
12~16h is impregnated in sour mixed aqueous solution, is cleaned up later with deionized water, and the aluminium flake of removal once oxidation film is obtained；
（a-3）Secondary oxidation：By step（a-2）The aluminium flake of obtained removal once oxidation film is placed in 0.3~0.5mol/L oxalic acid
In aqueous solution, 6~8h of electrochemical corrosion under the conditions of 80~90V of voltage, 0~3 DEG C of temperature, taking-up is cleaned with deionized water, then
It is placed in 1~3mol/LCuCl210~60min is impregnated in aqueous solution, is cleaned up later with deionized water, is obtained receiving containing bilateral
The alumina formwork of metre hole；
（a-4）Reaming：At 30~35 DEG C, by step（a-3）The obtained alumina formwork containing bi-pass nano hole is placed in 3~
5wt%H3PO420~45min of reaming in aqueous solution, obtains anodic oxidation aluminium formwork；
（b）Pulse electrodeposition nanotube
（b-1）Sputter conductive layer：By step（a-4）Gained anodic oxidation aluminium formwork is fixed in the fixture of magnetron sputtering, in argon
Gas velocity is 10~30sccm, and air pressure is 3~5 × 10-4Pa, automatic bias sputter one layer of copper film under conditions of being 150~200Pa；
（b-2）Pulse electrodeposition：Build three-electrode system, deposition potential be square-wave pulse potential, first 0V deposit 10~
15s, then add -3V 1~3s of potential deposition, it is recycled as one, deposition process carries out 164~492 cycles in total；
（c）Discharge nanotube
By step（b-2）The anodic oxidation aluminium formwork of electro-deposition, which is soaked in alkaline solution, removes alumina formwork and copper film,
Up to the magnetic metal nanotube.
2. the method that a kind of pulse electrodeposition according to claim 1 prepares magnetic metal nanotube, which is characterized in that step
Suddenly（a-1）Described in annealing aluminum sheet, supersound washing pretreatment be：Anneal 2~4h under the conditions of aluminium flake is first placed in 500 DEG C, connects
Ultrasound 10min in acetone, 5~10min is then impregnated in alkaline solution, finally 3~5min of ultrasound in acetone, it is described
Aluminium flake is the thin slice of 50~60 μ m thicks, and the electrochemical corrosion condition is 40~60V of voltage, 0~3 DEG C of temperature.
3. the method that a kind of pulse electrodeposition according to claim 2 prepares magnetic metal nanotube, which is characterized in that pre-
Alkaline solution described in processing is the sodium hydrate aqueous solution of 5wt%.
4. the method that a kind of pulse electrodeposition according to claim 1 or 2 prepares magnetic metal nanotube, feature exist
In step（a-2）Described in phosphoric acid and chromic acid mixed aqueous solution phosphoric acid concentration be 3~6wt%, a concentration of 1~2wt% of chromic acid.
5. the method that a kind of pulse electrodeposition according to claim 1 or 2 prepares magnetic metal nanotube, feature exist
In step（b-2）In constructed three-electrode system with step（b-1）The anodic oxidation aluminium formwork conduct of obtained sputtering copper film
It is auxiliary electrode that working electrode, platinized platinum, which are to electrode, saturated calomel electrode, and auxiliary electrode is immersed in saturation KCl solution, right
Electrode and working electrode impregnate in the electrolytic solution, then connect saturation KCl solution with salt bridge and electrolyte carries out electro-deposition, described
Contain the raw material of following parts by weight in salt bridge：0.95~1.0 part of agar, 8~12 parts of potassium chloride, 25~35 parts of deionized water.
6. the method that a kind of pulse electrodeposition according to claim 1 or 2 prepares magnetic metal nanotube, feature exist
In step（b-2）The electrolyte includes but not limited to：Nickel salt solution, cobalt salt solution and ferrous salt solution.
7. the method that a kind of pulse electrodeposition according to claim 6 prepares magnetic metal nanotube, which is characterized in that institute
It is dissolved with 300~400g/L NiSO to state nickel salt solution4•6H2O, 45~60g/L NiCl2•6H2O and 45~60g/L H3BO3's
Aqueous solution, nickel salt solution pH value are 3~5.
8. the method that a kind of pulse electrodeposition according to claim 6 prepares magnetic metal nanotube, which is characterized in that institute
It is dissolved with 300~400 g/L CoSO to state cobalt salt solution4•6H2O, 45~60 g/L CoCl2•6H2O and 45~60 g/L H3BO3
Aqueous solution, cobalt salt solution pH value be 3~5.
9. the method that a kind of pulse electrodeposition according to claim 6 prepares magnetic metal nanotube, which is characterized in that institute
It is dissolved with 300~400 g/L FeSO to state ferrous salt solution4•6H2O, 45~60 g/L FeCl2•6H2O, 15~30 g/L are anti-bad
Hematic acid and 45~60 g/L H3BO3Aqueous solution, ferrous salt solution pH value be 3~5.
10. the method that a kind of pulse electrodeposition according to claim 1 or 2 prepares magnetic metal nanotube, feature exist
In step（c）Described in alkaline solution be 5wt% sodium hydrate aqueous solutions, soaking time be 0.5~2h.
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