CN101016641A - Method of preparing three-dimensional aluminum oxide nano template by constant-current decompression - Google Patents
Method of preparing three-dimensional aluminum oxide nano template by constant-current decompression Download PDFInfo
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- CN101016641A CN101016641A CN 200610166555 CN200610166555A CN101016641A CN 101016641 A CN101016641 A CN 101016641A CN 200610166555 CN200610166555 CN 200610166555 CN 200610166555 A CN200610166555 A CN 200610166555A CN 101016641 A CN101016641 A CN 101016641A
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Abstract
The invention discloses a preparing method of three-dimensional aluminum oxide nanometer mold through constant-current decompression, which comprises the following steps: dealing surface; proceeding primary anodic oxidation; dissolving aluminum sheet of aluminum oxide; proceeding second anodic oxidation with electrical source as constant voltage mode; choosing the voltage from higher voltage to lower voltage with constant-current mode; keeping proper time till forming nanometer mold; making aluminum oxide nanometer hole on the surface of aluminum sheet occur bifurcation; sharing one opening to multiple; forming three-dimensional nanometer opening structure; controlling the bifurcated number of each opening with current. This method possesses convenient operation and low cost, which can be used to corresponding area widely.
Description
Technical field
The present invention relates to a kind ofly prepare the method for three-dimensional aluminum oxide template, belong to technical field of electrochemistry by constant-current decompression.
Background technology
As everyone knows, when the preparation nano material, need to use nanostructure template usually.Because alumina formwork is structurally ordered, can produce orderly nanostructure assembling system, and the preparation aluminium oxide nano-form simple to operate, cost is low, so, now use alumina formworks to prepare nano material more.The method that prepare at present the three-dimensional aluminum oxide template is by in the process of preparation template, progressively or linear reduction anodic oxidation voltage make the nano aperture generation bifurcated in the template and obtain 3-D nano, structure.But owing to electric current instability in the step-down process,, very likely can limit aluminium oxide nano-form, as the application of aspects such as electric transport process, an emission, fluorescence spectrum at some special dimensions so the bifurcation structure that obtains in this way is not in good order.
Summary of the invention
The objective of the invention is to overcome existing three-dimensional aluminum oxide nano template preparation method's deficiency, and provide a kind of method for preparing three-dimensional aluminum oxide nano template by constant-current decompression, this method can prepare the three-dimensional aluminum oxide nano template of high-sequential, the aluminium oxide nano-form of preparing has the microtexture more than a minute, and the bar number of bifurcated is adjustable.
Technical scheme provided by the invention is to adopt the following steps preparation under the envrionment temperature between 0 to 30 degree centigrade:
(1) to aluminium flake deoil successively, the processing of surface cleaning, electrochemical etching;
(2) do anode with the aluminium flake of handling, platinized platinum is cooked negative electrode, and aluminium flake is carried out an anodic oxidation with ordinary method, and once anodised number of times is 1 time, or carries out several repeatedly;
(3) pellumina with the aluminium flake surface after the anodic oxidation dissolves;
(4) be constant voltage mode with power settings earlier, aluminium flake after anodic oxidation under the constant voltage carries out anodic oxidation once more, and make voltage keep constant appropriate time abundant to its oxidation, constant voltage is between 0 volt to 200 volts, do not comprise 0 volt, be that anodic oxidation voltage is reduced between 0 volt to 140 volts gradually then with power settings, do not comprise 0 volt, and make the voltage after stablizing also keep constant appropriate time to nano-form to be completed into, promptly obtain three-dimensional aluminum oxide nano template, wherein after the step-down and the current ratio before the step-down should be between 0.05 to 0.5.
At last the three-dimensional aluminum oxide nano template that makes is inserted and remove in the saturated HgCl solution on the template behind the remaining aluminium, template is taken out cleaning and dry getting final product.
And during with the method for preparing three-dimensional aluminum oxide nano template, it is aluminium flake more than 98% that aluminium flake should be selected purity usually, envrionment temperature generally should be between 0 to 30 degree centigrade, and use acetone to deoil usually, rare strong acid and the rare strong base solution that is lower than 1mol/L with concentration carries out surface cleaning to aluminium flake respectively, is dissolved in the pellumina that the aluminium flake surface forms with the mixed solution of 4～10wt% phosphoric acid and 1～3wt% chromic acid.
The present invention is by changing the manufacturing process of three-dimensional aluminum oxide nano template, under constant current mode, changing to a lower voltage in the anode oxidation process once more from a higher voltage, because of square being inversely proportional to of the area density of aluminium oxide nano hole and anodised voltage, and voltage and electric current are one to one under the steady state.In the process of growth of alumina formwork, if reduction current density, the area density of aluminium oxide nano hole is increased, the number of hole increases, thereby make the nano aperture generation bifurcated in the template, the bar number of bifurcated is by the size decision of electric current, and the more little bifurcated of electric current is many more, form spatial three-D nano hole structure, this is a three-dimensional aluminum oxide nano template.Special with the nano material that this template is prepared owing to its structure, might there be special property at aspects such as electric transport process, an emission, fluorescence spectrums fully, thereby has wide practical use in association area.And the method for preparing three-dimensional aluminum oxide nano template provided by the invention also has low, the easy to operate advantage of cost.
Description of drawings
Fig. 1 is the side splitting figure of the three-dimensional aluminum oxide nano template example one of the present invention's preparation.
Fig. 2 is the pros and cons vertical view of the three-dimensional aluminum oxide nano template example one of the present invention's preparation.
Fig. 3 for the present invention the preparation example one the bifurcated process in, the layout viewing of bifurcated aperture.
Fig. 4 is the layout viewing of the present invention at preparation example one bottom surface aperture.
Fig. 5 for the present invention the preparation example two the bifurcated process in, the layout viewing of bifurcated aperture.
Embodiment
The method that the present invention prepares three-dimensional aluminum oxide nano template is after will be through surface treatment, an anodic oxidation under 0 ℃～30 ℃ the envrionment temperature and the aluminium flake that dissolves aluminum oxide carries out anodic oxidation once more, and anodic oxidation is to be earlier with the high voltage anodic oxidation under the constant voltage mode at power supply once more, use the constant current mode step-down then instead and be reduced to low voltage, also keep constant appropriate time to nano-form to be completed into.Used reaction conditionss such as electrolytic solution are determined according to a conventional method in the anode oxidation process once more.
Provide specific embodiment as follows below:
Embodiment one
In envrionment temperature is about 20 degrees centigrade, as follows operation:
(1) with thickness is the shape that the aluminium flake of 0.2mm is cut into 2.5cm * 3cm.
(2) use acetone to deoil, use 0.1mol/L dilute sulphuric acid and diluted sodium hydroxide solution to wash this aluminium flake then respectively.
(3) in the electrolytic solution of 80wt% raw spirit and 20wt% perchloric acid mixing solutions, the aluminium flake of handling is cooked anode, platinized platinum is cooked negative electrode and is carried out electrochemical etching, and voltage is 16v, 3 minutes time.
(4) use the oxalic acid of 0.3mol/L to do electrolytic solution, the aluminium flake after the polishing is cooked anode, and platinized platinum is cooked negative electrode, and aluminium flake is carried out anodic oxidation.Voltage 52v, 6 hours time.
(5) use the mixed solution of 6wt% phosphoric acid and 1.8wt% chromic acid to be dissolved in the pellumina that the aluminium flake surface forms.
(6) use oxalic acid to do electrolytic solution, under the constant voltage of 52v, carry out anodic oxidation 2 minutes once more.This moment, current density was 10mA/cm
2Current density is reduced to 2.6mA/cm
2And continue 90 seconds this moments voltage and reduced to 30v, keep 30v voltage and continue 12.5 minutes.
Embodiment two
(1)-(5) step is the same
(6) use oxalic acid to do electrolytic solution, under the constant voltage of 52v, carry out anodic oxidation 2 minutes once more.This moment, current density was 10mA/cm
2Current density is reduced to 2mA/cm
2And continue 120 seconds this moments voltage and reduced to 26v, keep 26v voltage and continue 12.5 minutes.
Embodiment three
In envrionment temperature is about 5 degrees centigrade, as follows operation:
(1) with thickness is the shape that the aluminium flake of 0.2mm is cut into 2.5cm * 3cm.
(2) use acetone to deoil, use 0.1mol/L dilute sulphuric acid and diluted sodium hydroxide solution to wash this aluminium flake then respectively.
(3) in the electrolytic solution of 80wt% raw spirit and 20wt% perchloric acid mixing solutions, the aluminium flake of handling is cooked anode, platinized platinum is cooked negative electrode and is carried out electrochemical etching, and voltage is 16v, 3 minutes time.
(4) use the sulfuric acid of 0.3mol/L to do electrolytic solution, the aluminium flake after the polishing is cooked anode, and platinized platinum is cooked negative electrode, and aluminium flake is carried out anodic oxidation.Voltage 20v, 6 hours time.
(5) use the mixed solution of 6wt% phosphoric acid and 1.8wt% chromic acid to be dissolved in the pellumina that the aluminium flake surface forms.
(6) use the sulfuric acid of 0.3mol/L to do electrolytic solution, under the constant voltage of 20v, carry out anodic oxidation one hour once more.This moment, current density was 4mA/cm
2Current density is reduced to 0.4mA/cm
2And continue 20 minutes this moments voltage and reduced to 3v, keep 3v voltage and continue 5 hours.
Embodiment four
In envrionment temperature is about 1 degree centigrade, as follows operation:
(1) with thickness is the shape that the aluminium flake of 0.2mm is cut into 2.5cm * 3cm.
(2) use acetone to deoil, use 0.1mol/L dilute sulphuric acid and diluted sodium hydroxide solution to wash this aluminium flake then respectively.
(3) in the electrolytic solution of 80wt% raw spirit and 20wt% perchloric acid mixing solutions, the aluminium flake of handling is cooked anode, platinized platinum is cooked negative electrode and is carried out electrochemical etching, and voltage is 16v, 3 minutes time.
(4) use the phosphoric acid of 0.1mol/L to do electrolytic solution, the aluminium flake after the polishing is cooked anode, and platinized platinum is cooked negative electrode, and aluminium flake is carried out anodic oxidation.Voltage 195v, 16 hours time.
(5) use the mixed solution of 6wt% phosphoric acid and 1.8wt% chromic acid to be dissolved in the pellumina that the aluminium flake surface forms.
(6) use the phosphoric acid of 0.1mol/L to do electrolytic solution, under the constant voltage of 195v, carry out anodic oxidation 5 hours once more.Current density is reduced to half, and also lasting 25 minutes this moments, voltage was reduced to 110v, kept 110v voltage also lasting 5 hours.
The finished product that embodiment one, two makes is analyzed, and to shown in Figure 5, Fig. 1 scale is 200nm as Fig. 1, and Fig. 2 to Fig. 5 scale is 100nm.It is three that Fig. 1 shows every original behind loss of voltage hole bifurcated, because three holes are not on plane, the same side, so only see mostly on the figure that a hole is branched into two.Light-colored part is an aluminum oxide among Fig. 2, and black part is divided into hole; Fig. 3 is in the bifurcated process, the arranging of bifurcated aperture.From can finding out clearly that here each macropore tells three apertures, and arrange in order.Figure four arranges for template bottom surface aperture.Can illustrate with method provided by the invention from this and can prepare orderly three-dimensional aluminum oxide nano template with one minute three structure.Figure five arranges for aperture in the example bifurcated process, and each macropore is divided into four as can be seen, illustrates that the bar number of every hole bifurcated can pass through current control.
Claims (5)
1, a kind ofly prepare the method for three-dimensional aluminum oxide nano template, it is characterized in that under the envrionment temperature between 0 to 30 degree centigrade, adopting the following steps preparation by constant-current decompression:
(1) to aluminium flake deoil successively, the processing of surface cleaning, electrochemical etching;
(2) do anode with the aluminium flake of handling, platinized platinum is cooked negative electrode, and aluminium flake is carried out an anodic oxidation with ordinary method, and once anodised number of times is 1 time, or carries out several repeatedly;
(3) pellumina with the aluminium flake surface after the anodic oxidation dissolves;
(4) be constant voltage mode with power settings earlier, aluminium flake after anodic oxidation under the constant voltage carries out anodic oxidation once more, and make voltage keep constant appropriate time abundant to its oxidation, constant voltage is between 0 volt to 200 volts, do not comprise 0 volt, be that anodic oxidation voltage is reduced between 0 volt to 140 volts gradually then with power settings, do not comprise 0 volt, and make the voltage after stablizing also keep constant appropriate time to nano-form to be completed into, promptly obtain three-dimensional aluminum oxide nano template, wherein after the step-down and the current ratio before the step-down should be between 0.05 to 0.5.
2, the method for preparing three-dimensional aluminum oxide nano template by constant-current decompression according to claim 1, it is characterized in that: the three-dimensional aluminum oxide nano template that makes is inserted remove in the saturated HgCl solution on the template behind the remaining aluminium at last, template is taken out cleaning and dry.
3, according to claim 1 and 2ly prepare the method for three-dimensional aluminum oxide nano template by constant-current decompression, it is characterized in that: used aluminium flake is that purity is the aluminium flake more than 98%.
4, the method for preparing three-dimensional aluminum oxide nano template by constant-current decompression according to claim 1 and 2, it is characterized in that: use acetone to deoil, with dilute sulphuric acid and diluted sodium hydroxide solution aluminium flake is carried out surface cleaning respectively, the concentration of dilute sulphuric acid and dilute sodium hydroxide is below 1mol/l.
5, according to claim 1 and 2ly prepare the method for three-dimensional aluminum oxide nano template, it is characterized in that: use the mixed solution of 4～10wt% phosphoric acid and 1～3wt% chromic acid to be dissolved in the pellumina that the aluminium flake surface forms by constant-current decompression.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838835A (en) * | 2010-03-30 | 2010-09-22 | 同济大学 | Ordered porous alumina template capable of being directly applied to electrochemical deposition and preparation method thereof |
| CN101851771A (en) * | 2010-06-11 | 2010-10-06 | 同济大学 | Ordered porous alumina template capable of being directly used in electrochemical deposition and production method |
| CN101928972A (en) * | 2010-07-23 | 2010-12-29 | 北京航空航天大学 | Method for preparing nickel-polypyrrole double-layer nanowire array material |
| CN102560650A (en) * | 2010-12-29 | 2012-07-11 | 中国科学院合肥物质科学研究院 | Porous aluminum oxide photonic crystal and preparation method and applications thereof |
| CN103173832A (en) * | 2013-04-25 | 2013-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel aluminum material with microscale self-driven dropwise condensation function and preparation method thereof |
| CN106068338A (en) * | 2014-02-28 | 2016-11-02 | 株式会社樱花彩色笔 | Coloring aluminium formed body and manufacture method thereof |
| CN109208055A (en) * | 2017-06-30 | 2019-01-15 | 比亚迪股份有限公司 | A kind of aluminium alloy and preparation method thereof and handset shell |
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2006
- 2006-12-31 CN CN200610166555A patent/CN100588754C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838835A (en) * | 2010-03-30 | 2010-09-22 | 同济大学 | Ordered porous alumina template capable of being directly applied to electrochemical deposition and preparation method thereof |
| CN101851771A (en) * | 2010-06-11 | 2010-10-06 | 同济大学 | Ordered porous alumina template capable of being directly used in electrochemical deposition and production method |
| CN101928972A (en) * | 2010-07-23 | 2010-12-29 | 北京航空航天大学 | Method for preparing nickel-polypyrrole double-layer nanowire array material |
| CN101928972B (en) * | 2010-07-23 | 2011-11-09 | 北京航空航天大学 | Method for preparing nickel-polypyrrole double-layer nanowire array material |
| CN102560650A (en) * | 2010-12-29 | 2012-07-11 | 中国科学院合肥物质科学研究院 | Porous aluminum oxide photonic crystal and preparation method and applications thereof |
| CN102560650B (en) * | 2010-12-29 | 2014-10-22 | 中国科学院合肥物质科学研究院 | Porous aluminum oxide photonic crystal and preparation method and applications thereof |
| CN103173832A (en) * | 2013-04-25 | 2013-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel aluminum material with microscale self-driven dropwise condensation function and preparation method thereof |
| CN103173832B (en) * | 2013-04-25 | 2015-12-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | There is aluminium of the self-driven drop-wise condensation function of microscale and preparation method thereof |
| CN106068338A (en) * | 2014-02-28 | 2016-11-02 | 株式会社樱花彩色笔 | Coloring aluminium formed body and manufacture method thereof |
| CN109208055A (en) * | 2017-06-30 | 2019-01-15 | 比亚迪股份有限公司 | A kind of aluminium alloy and preparation method thereof and handset shell |
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| CN100588754C (en) | 2010-02-10 |
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