CN100412237C - Manufacturing method of three dimensional aluminium oxide nanometer pattern plate - Google Patents
Manufacturing method of three dimensional aluminium oxide nanometer pattern plate Download PDFInfo
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- CN100412237C CN100412237C CNB200510018403XA CN200510018403A CN100412237C CN 100412237 C CN100412237 C CN 100412237C CN B200510018403X A CNB200510018403X A CN B200510018403XA CN 200510018403 A CN200510018403 A CN 200510018403A CN 100412237 C CN100412237 C CN 100412237C
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Abstract
The present invention discloses a manufacturing method of a three-dimensional aluminum oxide nanometer template. In the manufacturing method of a three-dimensional aluminum oxide nanometer template, an anode of an aluminum piece after a surface treating process, an anode oxidizing process and an aluminum oxide dissolving process is oxidized again. In the second anode oxidizing process, the anode oxidation of high voltage is lowered to the anode oxidation of low voltage, an aluminum oxide nanometer hole formed on the surface of the aluminum piece can be branched, and one hole is divided into three holes in different planes; therefore, a three-dimensional nanometer hole structure is formed. The manufacturing method of a three-dimensional aluminum oxide nanometer template has the advantages of convenient operation and low manufacturing cost, the structure of the three-dimensional aluminum oxide nanometer template prepared by the manufacturing method of a three-dimensional aluminum oxide nanometer template is particular, and the three-dimensional aluminum oxide nanometer template can completely possibly have particular property in the aspects of electric transporting processes, field emission, ultraviolet spectrums, etc. Therefore, the three-dimensional aluminum oxide nanometer template prepared by the present invention has wide application prospect in relevant fields.
Description
Technical field
The present invention relates to a kind of preparation method of three-dimensional aluminum oxide nano template, belong to technical field of electrochemistry.
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, at present use alumina formworks to prepare nano material more.But the now used electrochemical deposition of people, electroless plating, vapour deposition etc. prepare 1-dimention nano piping material and array thereof that the method for aluminium oxide nano-form can only be prepared length and controllable diameter, existing these preparation methods can't make the aluminium oxide nano-form with other microtexture, therefore also can limit aluminium oxide nano-form most probably at some special dimensions, as the application of aspects such as electric transport process, an emission, UV spectrum.
Summary of the invention
In order to overcome the deficiency that existing method can only prepare the one dimension aluminium oxide nano-form, the invention provides a kind of method that can prepare three-dimensional aluminum oxide nano template, the aluminium oxide nano-form for preparing with this method has one minute three microtexture, and the order degree height.
The scheme that the present invention deals with problems is suitably to adopt following steps to prepare under the envrionment temperature:
(1) to aluminium flake successively with ordinary method deoil, the processing of surface cleaning, electrochemical etching, anodic oxidation, dissolved oxygen aluminium film.
(2) aluminium flake that will handle under constant voltage carries out anodic oxidation once more, and makes voltage keep constant appropriate time abundant to oxidation, and voltage is chosen between 40 volts to 65 volts.
(3) speed with 0.1v/s～3v/s drops to voltage between 25 volts to 40 volts, and makes the voltage after the reduction also keep constant appropriate time to nano-form to be completed into, and promptly obtains three-dimensional aluminum oxide nano template.
At last the three-dimensional aluminum oxide nano template that makes is inserted and remove in the saturated mercuric chloride solution on the template behind the remaining aluminium, template is taken out cleaning and dry getting final product.
Wherein, the ratio of the middle applied voltage of step (2) applied voltage and step (3) is between 1.5: 1 to 2.0: 1.
During with the method for preparing three-dimensional aluminum oxide nano template, aluminium flake should be selected the higher aluminium flake of 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, use the oxalic acid of 0.2-0.5mol/L to do electrolytic solution, aluminium flake after the polishing is cooked anode, platinized platinum is cooked negative electrode, aluminium flake is carried out anodic oxidation, be dissolved in the pellumina of aluminium flake surface formation with the mixed solution of 4～10wt% phosphoric acid and 1～3wt% chromic acid.
The present invention is by changing the manufacturing process of one dimension aluminium oxide nano-form, in anode oxidation process, change to a lower voltage from a higher voltage, because of square being inversely proportional to of the area density of aluminium oxide nano hole and anodised voltage, in the process of growth of alumina formwork, if reduction anodic oxidation voltage, 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, every hole is several by a bifurcated, 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, UV spectrum 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 front plan view of the three-dimensional aluminum oxide nano template of the present invention's preparation.
Fig. 2 is the side splitting figure of the three-dimensional aluminum oxide nano template of the present invention's preparation.
Fig. 3 is the reverse side vertical view of the three-dimensional aluminum oxide nano template of the present invention's preparation.
Embodiment
The method that the present invention prepares three-dimensional aluminum oxide nano template is operation as follows under 0 ℃～30 ℃ envrionment temperature:
Step 1: with a purity reach as high as 99.99% aluminium flake successively through deoiling, rare strong acid cleans, rare highly basic cleans, electrochemical etching, thereby form the surface of cleaning light.
Step 2: use the oxalic acid of 0.2-0.5mol/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 once or anodic oxidation for several times, uses the mixed solution of phosphoric acid and chromic acid to be dissolved in the pellumina that the aluminium flake surface forms then.
Step 3: carry out anodic oxidation once more, and it is abundant to oxidation to make voltage continue appropriate time under the constant voltage between 40v～60V.
Step 4: with the speed between 0.1v/s～3v/s, voltage is dropped to a magnitude of voltage between 40v～25v, the ratio of constant voltage and this voltage should be between 1.5: 1 to 2.0: 1 in the step 3, and this voltage is continued appropriate time to nano-form are completed into.
Step 5: use saturated mercuric chloride solution to dissolve aluminium on the alumina formwork.
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, working concentration is that dilute sulphuric acid and the diluted sodium hydroxide solution of 0.3mol/L washs this aluminium flake respectively then.
(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 40 minutes once more.Speed with 0.5v/s reduces the voltage to 30v then, is fixed on 30v then, continues 80 minutes.
(7) prepared three-dimensional aluminum oxide nano template is inserted remove remaining aluminium on the template in the saturated mercuric chloride solution, alumina formwork is taken out cleaning and dry.
Embodiment two
In envrionment temperature is about 15 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, working concentration is that dilute sulphuric acid and the diluted sodium hydroxide solution of 0.3mol/L washs this aluminium flake respectively then.
(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 60v, 3 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 60v constant voltage, carry out anodic oxidation 40 minutes once more.Speed with 0.3v/s reduces the voltage to 35v then, is fixed on 35v then, continues 80 minutes.
(8) prepared three-dimensional aluminum oxide nano template is inserted remove remaining aluminium on the template in the saturated mercuric chloride solution, alumina formwork is taken out cleaning and dry.
Embodiment three
In envrionment temperature is about 10 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, working concentration is that dilute sulphuric acid and the diluted sodium hydroxide solution of 0.3mol/L washs this aluminium flake respectively then.
(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 40v, 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 40v, carry out anodic oxidation 40 minutes once more.Speed with 0.1v/s reduces the voltage to 23v then, is fixed on 23v then, continues 80 minutes.
(7) prepared three-dimensional aluminum oxide nano template is inserted remove remaining aluminium on the template in the saturated mercuric chloride solution, alumina formwork is taken out cleaning and dry.
The finished product that embodiment one makes is analyzed, and as Fig. 1, Fig. 2, shown in Figure 3, each figure scale is 100nm, and light-colored part is an aluminum oxide among the figure, and black part is divided into hole, and hole diameter is 60nm among Fig. 1; It is three that Fig. 2 shows every original behind loss of voltage hole bifurcated, because three holes are not at grade, so only see mostly on the figure that a hole is branched into two, the little figure in the lower left corner is that a hole is branched into three special case on the splitting figure; Hole diameter among Fig. 3 is 35nm, and hole density is three times among the figure (1); Can illustrate with method provided by the invention from this three width of cloth figure and can prepare three-dimensional aluminum oxide nano template with one minute three structure.
Claims (6)
1. the preparation method of a three-dimensional aluminum oxide nano template is characterized in that adopting the following steps preparation under suitable envrionment temperature:
(1) to aluminium flake successively with corresponding ordinary method deoil, the processing of surface cleaning, electrochemical etching;
(2) aluminium flake of handling is carried out anodic oxidation with ordinary method, anodised number of times can be 1 time, also can carry out several repeatedly;
(3) with the pellumina dissolving on the aluminium flake surface of ordinary method after with anodic oxidation;
(4) aluminium flake that will handle under constant voltage carries out anodic oxidation once more, and makes voltage keep constant appropriate time abundant to oxidation, and voltage is chosen between 40 volts to 65 volts;
(5) speed with 0.1v/s～3v/s drops to voltage between 25 volts to 40 volts, and make the voltage after the reduction also keep constant appropriate time to nano-form to be completed into, promptly obtain three-dimensional aluminum oxide nano template, and the ratio of applied voltage should be between 1.5: 1 to 2.0: 1 in step (4) applied voltage and this step.
2. the preparation method of three-dimensional aluminum oxide nano template according to claim 1 is characterized in that: the three-dimensional aluminum oxide nano template that makes is inserted remove in the saturated mercuric chloride solution on the template behind the remaining aluminium at last, template is taken out cleaning and dry.
3. the preparation method of three-dimensional aluminum oxide nano template according to claim 1 and 2, it is characterized in that: use acetone to deoil, with rare strong acid and rare strong base solution aluminium flake is carried out surface cleaning respectively, the concentration of rare strong acid and rare strong base solution is below 1mol/l.
4. according to the preparation method of claim 1 or 2 described three-dimensional aluminum oxide nano templates, it is characterized in that: use the oxalic acid of 0.2-0.5mol/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.
5. the preparation method of three-dimensional aluminum oxide nano template according to claim 1 and 2 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.
6. the preparation method of three-dimensional aluminum oxide nano template according to claim 1 and 2, it is characterized in that: envrionment temperature is between 0 to 30 degree centigrade.
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| CN100441348C (en) * | 2006-05-12 | 2008-12-10 | 天津大学 | Metal nano nickel tube 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 |
| ES2559275B1 (en) * | 2014-07-11 | 2016-11-22 | Consejo Superior De Investigaciones Científicas (Csic) | Nanostructured MATERIAL, PROCESS FOR OBTAINING AND USING THE SAME |
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| CN1041708A (en) * | 1988-10-03 | 1990-05-02 | 艾尔坎国际有限公司 | Porous anodic aluminium oxide membranes |
| US6325909B1 (en) * | 1999-09-24 | 2001-12-04 | The Governing Council Of The University Of Toronto | Method of growth of branched carbon nanotubes and devices produced from the branched nanotubes |
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| US4687551A (en) * | 1984-10-17 | 1987-08-18 | Alcan International Limited | Porous films and method of forming them |
| CN1041708A (en) * | 1988-10-03 | 1990-05-02 | 艾尔坎国际有限公司 | Porous anodic aluminium oxide membranes |
| US6325909B1 (en) * | 1999-09-24 | 2001-12-04 | The Governing Council Of The University Of Toronto | Method of growth of branched carbon nanotubes and devices produced from the branched nanotubes |
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