CN103031583A - Preparation method of nickel nano-wire in one-dimensional closed-packed hexagonal crystal structure - Google Patents
Preparation method of nickel nano-wire in one-dimensional closed-packed hexagonal crystal structure Download PDFInfo
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- CN103031583A CN103031583A CN2012101748345A CN201210174834A CN103031583A CN 103031583 A CN103031583 A CN 103031583A CN 2012101748345 A CN2012101748345 A CN 2012101748345A CN 201210174834 A CN201210174834 A CN 201210174834A CN 103031583 A CN103031583 A CN 103031583A
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Abstract
The invention relates to a preparation method of a nickel nano-wire in a one-dimensional closed-packed hexagonal crystal structure. The preparation method comprises the following steps of: A. preparing template: preparing a template with through holes which are uniformly distributed, wherein the template comprises an alumina template, an aniline template and a polypeptide film; and B. conducting direction current electrodeposition: b1. conducting direction current electrodeposition: sputtering a layer of silver on one surface of the alumina template prepared in step a4 as a cathode, using a metal to be plated as an anode, putting the metal to be plated into an electroplating bath, and using a saline solution of the metal to be plated as an electroplating solution; and b2. conducting parameter control: adding a set voltage between the cathode and the anode in the step b1, keeping the current of a circuit constant to rang from 2V to 4V and controlling the deposition time to obtain a closed-packed hexagonal metal nano-wire array which grows in each template hole.
Description
Technical field
The invention belongs to the preparing technical field of magnetic one-dimensional nano line array, relate to a kind of preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire.
Background technology
Compare the nickel (Ni) of face-centered cubic (fcc) crystalline structure, the nickel (Ni) of close-packed hexagonal (hcp) crystalline structure because energy higher be a kind of non-steady phase, can not stable existence at occurring in nature.Yet just because of the energy height is unstable, when changing, stable phase can emit energy.Therefore utilize these characteristics may develop the phase transition energy switching device.
Close-packed hexagonal nickel (referred to as hcpNi) is found in the alloy firm of rapid solidification formation mutually at first, and the report of the synthetic hcpNi phase nano particle of hydrothermal method is arranged again subsequently.
HcpNi in the alloy firm is separated very difficult, and the hcpNi phase size in the nano particle is very little, and process of growth is restive, therefore needs the new method of exploitation to prepare the material of hcpNi phase.
Summary of the invention
The object of the invention is to, a kind of preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire is provided, be separated very difficult with the nickel that overcomes the Patterns for Close-Packed Hexagonal Crystal structure in the existing alloy firm of prior art, the nickel phase size of the Patterns for Close-Packed Hexagonal Crystal structure in the nano particle is very little, the shortcoming and defect that process of growth is restive.
Principle of work of the present invention: by plating solution formula and the processing parameter of choose reasonable, the hcpNi nano wire is prepared in galvanic deposit.
The present invention utilizes electrochemical method, choose reasonable plating solution formula and processing parameter, the nickel nano wire that preparation has the Patterns for Close-Packed Hexagonal Crystal structure in the alumina formwork hole.This method is simple, and controllability is very strong.
The technical problem that will solve required for the present invention can be achieved through the following technical solutions:
The preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire may further comprise the steps:
A, template:
Preparation has the template of equally distributed through hole, and described template comprises: alumina formwork, many carbon films;
B, dc electrodeposition:
B1, dc electrodeposition: as negative electrode, plating metal is made anode, puts into plating tank with the one side sputter last layer silver of template, and the plating metal salts solution is electroplate liquid; And
The control of b2, parameter: between the negative electrode of step b1, anode, add the voltage of setting, the retaining circuit voltage constant, the control depositing time namely obtains being grown in the nickel nano-wire array of the Patterns for Close-Packed Hexagonal Crystal structure in the pattern hole.
Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have such feature: the preparation process of described alumina formwork may further comprise the steps:
A1, for the first time anodic oxidation: the aluminium flake after the polishing of deoiling is as anode, and copper is to electrode, and in acid electrolyte, temperature remains on 0 ℃.Inter-electrode voltage is 40V, and anodic oxidation 12h is at the Surface Creation alumina layer of aluminium flake;
A2, the first time are removed alumina layer: adopt chromic acid and phosphoric acid mixing solutions to remove the alumina layer of generation, clean;
A3, for the second time anodic oxidation: step a2 is removed aluminium flake behind the alumina layer as anode, copper is negative electrode, carry out the anodic oxidation second time, in acid electrolyte, temperature remains on 0 ℃, and inter-electrode voltage is 40V, anodizing time is 2 ~ 3h, after for the second time anodic oxidation, the aluminium flake surface just forms even distribution alumina pore channel array, in bottom, duct and aluminium flake junction the thin blocking layer of one deck is arranged; And
A4, remove blocking layer and reaming: adopt the acid chlorization copper solutions to remove remaining alumina layer, described acid chlorization copper solutions is 15g CuCl
2+ 30ml 35wt% hydrochloric acid+270ml water; Then go to the blocking layer with the 5wt% phosphoric acid solution, clean, oven dry forms the alumina formwork with equally distributed through hole;
Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have among such feature: step a1 and the a3, and described electrolytic solution adopts any of phosphoric acid, oxalic acid, sulfuric acid.
Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have such feature: according to weight ratio, among the step a2, according to weight ratio, the volume ratio of described 15wt% chromic acid and 10wt% phosphoric acid is 1:5.
Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have such feature: among the step a3, described anodizing time is 2h.Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have such feature: among the step b1, anode is nickel, and described electroplate liquid contains 220g/l NiSO
46H
2O, 30g/l NiCl
2And 10g/lH
3BO
3
Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have such feature: among the step b2, and described depositing time 1～10min.
Further, the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire of the present invention can also have such feature: among the step b2, described voltage constant is in a certain value of voltage constant between 2 ~ 4V.
Beneficial effect of the present invention:
The present invention forms plating solution formula and processing parameter improvement process on original electrochemical deposition basis, has simple characteristics.
The close-packed hexagonal nickel nano wire that the present invention makes can whole nano wire all be the hcp crystalline structure.
Dc electrodeposition process and existing dc electrodeposition technology, but electrolyte prescription and processing parameter from deposition technique was different in the past, difference is, adopts high Ni
2+The concentration plating solution formula, the generation of plated electrode bubble when high overpotential is treated in control, and high overpotential has produced the non-six side's nickel of surely arranging mutually with higher-energy.
Description of drawings
Fig. 1 is the low power pattern photo of Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire, and illustration is corresponding selected area electron diffraction.
The diffraction that Fig. 2 obtains for the high resolution photo corresponding with Fig. 1 and corresponding Fourier transform.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples are only for explanation the present invention but not for limiting scope of the present invention.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition that manufacturer provides is carried out.
Embodiment
It is that dc electrodeposition in pattern hole prepares the Ni nano wire by choose reasonable electroplate liquid and galvanic deposit parameter that the present invention prepares nano wire.Comprise that preparation has template and two processes of dc electrodeposition of equally distributed through hole.
The preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire adopts the alumina formwork dc electrodeposition, specifically may further comprise the steps:
A, template:
Preparation has the template of equally distributed through hole, and template comprises: alumina formwork, many carbon films.
Wherein, many carbon films are commercially available.
Embodiment 1 is take alumina formwork as example, and the preparation process of alumina formwork may further comprise the steps:
A1, for the first time anodic oxidation: the aluminium flake after the polishing of deoiling is as anode, and copper is to electrode, and electrolytic solution adopts phosphoric acid, and temperature remains on 0 ℃.Inter-electrode voltage is 40V, and anodic oxidation 12h is at the Surface Creation alumina layer of aluminium flake.
A2, the first time are removed alumina layer: according to weight ratio, adopting the volume ratio of chromic acid 15wt% and phosphatase 11 0wt% is the alumina layer that the 1:5 mixed solution is removed generation, cleans.
A3, for the second time anodic oxidation: step a2 is removed aluminium flake behind the alumina layer as anode, and copper is negative electrode, carries out the anodic oxidation second time, and in acid electrolyte, temperature remains on 0 ℃, and inter-electrode voltage is 40V, anodic oxidation 2 ~ 3h.
After for the second time anodic oxidation, the aluminium flake surface just forms even distribution alumina pore channel array, in bottom, duct and aluminium flake junction the thin blocking layer of one deck is arranged.
A4, remove blocking layer and reaming: adopt the acid chlorization copper solutions to remove remaining alumina layer, go to the blocking layer with the 5wt% phosphoric acid solution, clean, oven dry, formation has the alumina formwork of equally distributed through hole.
Wherein, acid chlorization copper solutions 15g CuCl
2Analytical pure+30ml 35wt% hydrochloric acid analytical pure+270ml water.
Among step a1 and the a3, acid electrolyte can also adopt any of sulfuric acid, oxalic acid except phosphoric acid.
B, dc electrodeposition:
B1, dc electrodeposition: the one side sputter last layer silver of the alumina formwork that step a4 is made is as negative electrode, and plating metal is made anode, is nickel such as anode, puts into plating tank, and the plating metal salts solution is electroplate liquid, and electroplate liquid contains 220g/l NiSO
46H
2O, 30g/l NiCl
2And 10g/l H
3BO
3
The control of b2, parameter: between the negative electrode of step b1, anode, add the voltage of setting, a certain value of retaining circuit voltage constant between 2 ~ 4V, the control depositing time namely obtains being grown in the hexagonal closed-packed nano-wire array in the alumina formwork hole.
Nanowire length can be controlled by depositing time length.Among the step b2, depositing time 1～10min of embodiment 1.
The product of table 1 the present invention preparation and the comparison of prior art
Fig. 1 is the low power pattern photo of Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire, and illustration is corresponding selected area electron diffraction.The diffraction that Fig. 2 obtains for the high resolution photo corresponding with Fig. 1 and corresponding Fourier transform.As depicted in figs. 1 and 2, the pattern photo of two nickel nano wires and corresponding electron diffraction, the nickel nanowire surface that as seen makes is smooth and for the Patterns for Close-Packed Hexagonal Crystal structure.
Embodiment 1 is preferred embodiment of the present invention, and voltage constant is at 4V.Nanowire length can be controlled by depositing time length.Be 1min such as depositing time, the Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire that obtains is referring to Fig. 1 and Fig. 2.
More than the specific embodiment of the present invention is illustrated, but the present invention is as limit, only otherwise break away from aim of the present invention, the present invention can also have various variations.
Claims (8)
1. the preparation method of one dimension Patterns for Close-Packed Hexagonal Crystal structure nickel nano wire may further comprise the steps:
A, template:
Preparation has the template of equally distributed through hole, and described template comprises: alumina formwork, polypeptide films;
B, dc electrodeposition:
B1, dc electrodeposition: as negative electrode, plating metal is made anode, puts into plating tank with the one side sputter last layer silver of template, and the plating metal salts solution is electroplate liquid; And
The control of b2, parameter: between the negative electrode of step b1, anode, add the voltage of setting, the retaining circuit voltage constant, the control depositing time namely obtains being grown in the nickel nano-wire array of the Patterns for Close-Packed Hexagonal Crystal structure in the pattern hole.
2. preparation method according to claim 1 is characterized in that, the preparation process of described alumina formwork may further comprise the steps:
A1, for the first time anodic oxidation: the aluminium flake after the polishing of deoiling is as anode, and copper is to electrode, and in acid electrolyte, temperature remains on 0 ℃, and inter-electrode voltage is 40V, and anodic oxidation 12h is at the Surface Creation alumina layer of aluminium flake;
A2, the first time are removed alumina layer: adopt chromic acid and phosphoric acid mixing solutions to remove the alumina layer of generation, clean;
A3, for the second time anodic oxidation: step a2 is removed aluminium flake behind the alumina layer as anode, copper is negative electrode, carry out the anodic oxidation second time, in acid electrolyte, temperature remains on 0 ℃, and inter-electrode voltage is 40V, anodizing time is 2 ~ 3h, after for the second time anodic oxidation, the aluminium flake surface just forms even distribution alumina pore channel array, in bottom, duct and aluminium flake junction the thin blocking layer of one deck is arranged; And
A4, remove blocking layer and reaming: adopt the acid chlorization copper solutions to remove remaining alumina layer, described acid chlorization copper solutions is 15gCuCl
2+ 30ml 35wt% hydrochloric acid+270ml water; Then go to the blocking layer with the 5wt% phosphoric acid solution, clean, oven dry forms the alumina formwork with equally distributed through hole.
3. preparation method according to claim 2 is characterized in that, among step a1 and the a3, described electrolytic solution adopts any of phosphoric acid, oxalic acid, sulfuric acid.
4. preparation method according to claim 2 is characterized in that, among the step a2, according to weight ratio, the volume ratio of described 15wt% chromic acid and 10wt% phosphoric acid is 1:5.
5. preparation method according to claim 2 is characterized in that, among the step a3, described anodizing time is 2h.
6. preparation method according to claim 1 is characterized in that, among the step b1, anode is nickel, and described electroplate liquid contains 220g/l NiSO
46H
2O, 30g/l NiCl
2And 10g/l H
3BO
3
7. preparation method according to claim 1 is characterized in that, among the step b2, and depositing time 1～10min.
8. preparation method according to claim 1 is characterized in that, among the step b2, and a certain value of voltage constant between 2 ~ 4V.
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Cited By (3)
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|---|---|---|---|---|
| CN105603469A (en) * | 2015-12-23 | 2016-05-25 | 中国石油大学(北京) | CuO/Ni core-shell nanowire and preparation method thereof |
| CN108091579A (en) * | 2017-12-22 | 2018-05-29 | 哈尔滨工业大学 | A kind of method that electro-deposition prepares high-density electronic package vertical interconnection substrate |
| CN117512595A (en) * | 2024-01-08 | 2024-02-06 | 兰州大学 | Method for preparing elliptic magnetic nanowire with large length-diameter ratio and small size |
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| CN101007645A (en) * | 2006-01-23 | 2007-08-01 | 中国科学院化学研究所 | Process for preparing highly-hydrophilic alumina film material |
| CN101499417A (en) * | 2008-01-30 | 2009-08-05 | 中国科学院半导体研究所 | Method for implementing image transfer on semiconductor material by anodised aluminum template |
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| CN101007645A (en) * | 2006-01-23 | 2007-08-01 | 中国科学院化学研究所 | Process for preparing highly-hydrophilic alumina film material |
| CN101499417A (en) * | 2008-01-30 | 2009-08-05 | 中国科学院半导体研究所 | Method for implementing image transfer on semiconductor material by anodised aluminum template |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603469A (en) * | 2015-12-23 | 2016-05-25 | 中国石油大学(北京) | CuO/Ni core-shell nanowire and preparation method thereof |
| CN108091579A (en) * | 2017-12-22 | 2018-05-29 | 哈尔滨工业大学 | A kind of method that electro-deposition prepares high-density electronic package vertical interconnection substrate |
| CN117512595A (en) * | 2024-01-08 | 2024-02-06 | 兰州大学 | Method for preparing elliptic magnetic nanowire with large length-diameter ratio and small size |
| CN117512595B (en) * | 2024-01-08 | 2024-06-07 | 兰州大学 | Method for preparing elliptic magnetic nanowire with large length-diameter ratio and small size |
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