CN103484915A - Preparation method of uniform-aperture anodized aluminum template - Google Patents
Preparation method of uniform-aperture anodized aluminum template Download PDFInfo
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- CN103484915A CN103484915A CN201210197115.5A CN201210197115A CN103484915A CN 103484915 A CN103484915 A CN 103484915A CN 201210197115 A CN201210197115 A CN 201210197115A CN 103484915 A CN103484915 A CN 103484915A
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Abstract
The invention discloses a preparation method of a uniform-aperture anodized aluminum template. The preparation method which adopts a secondary anodizing process comprises the following steps: 1, placing an aluminum sheet in an oxalic acid solution having a concentration of 0.2-0.4mol/L, anodizing under a direct current voltage of 20-60V for at least 2h, and immersing the aluminum sheet in a phosphoric acid and chromic acid mixed solution having a temperature of 58-62DEG C for at least 3h to obtain an intermediate; and 2, placing the intermediate in a constant temperature oxalic acid solution having a concentration of 0.2-0.4mol/L and a temperature of 4-20DEG C, and anodizing under a direct current characterized by an initial voltage of 20-60V, a voltage build-up rate of +0.1-25V/h and a final voltage of 25-65V to prepare the uniform-aperture anodized aluminum template. The uniform-aperture anodized aluminum template has a thickness of 2-100mum, and the apertures of through holes are uniform apertures of 20-80nm. The preparation method reduces the preparation complexity and cost, reduces the environment pollution, and can be used for preparing uniform-aperture porous anodized aluminum templates.
Description
Technical field
The present invention relates to a kind of preparation method of alumina formwork, especially a kind of preparation method of anodic oxidation aluminium formwork of homogeneous aperture structure.
Background technology
Porous anodic alumina template is because of its unique structure and good chemical stability, become a kind of desirable mould material, by the various metals of deposition, alloy, semi-conductor, conductive polymers etc. in the nanoporous to template, can prepare various quasi-one-dimensional nano materials.In the recent period, people are in order to obtain porous anodic alumina template, various effort have been made, as a kind of " mixed acid electrolyte prepares the method for the porous anodic alumina template of high-sequential " disclosed in disclosed Chinese invention patent application prospectus CN 1793437A on June 28th, 2006.The preparation method who mentions in this specification sheets is usingd the mixing acid of sulfuric acid and oxalic acid as electrolytic solution, after the aluminium sample is carried out to oil removing, removing oxide layer, electrochemical polishing treatment successively, it is carried out to two step anodic oxidations, obtains porous anodic alumina template.Yet, though this preparation method has reduced the oxidation voltage for preparing porous anodic alumina template, reduced the thickness on porous anodic alumina template blocking layer, and the order that has improved nanohole array, but to using the mixing acid of two kinds of acid to realize as electrolytic solution, this has increased the complicacy of preparation undoubtedly, has aggravated the pollution of environment and has caused the increase of preparation cost.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming shortcoming part of the prior art, provides the preparation method of the anodic oxidation aluminium formwork of the homogeneous aperture structure that a kind of anodic oxidation voltage is compensatory voltage waveform.
For solving technical problem of the present invention, the technical scheme adopted is: the preparation method of the anodic oxidation aluminium formwork of homogeneous aperture structure adopts the two-step anodization method, and particularly completing steps is as follows:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.2～0.4mol/L, and under the volts DS of 20～60V, anode is oxidizing to few 2h, then be placed in the phosphorus chromic acid mixing solutions under 58～62 ℃ and soak at least 3h, obtains intermediate product;
20～80nm that the bore dia that the thickness of the anodic oxidation aluminium formwork of described homogeneous aperture structure is 2～100 μ m, clear opening is the homogeneous aperture.
As the preparation method's of the anodic oxidation aluminium formwork of homogeneous aperture structure further improvement, the purity of described aluminium flake is>=99.9%; Described before aluminium flake is carried out to anodic oxidation, first it alternately is placed in to ethanol and acetone ultrasonic cleaning 2～3 times, then dries after with deionized water, it being cleaned repeatedly, afterwards, being placed on vacuum tightness is 10
-5pa, temperature are the 5h that anneals under 500 ℃; Anodizing time in described step 1 is 2～6h; The chromic acid configuration that the phosphoric acid that described phosphorus chromic acid mixing solutions is 6wt% by concentration and concentration are 1.5wt% forms.
Beneficial effect with respect to prior art is, one, anodic oxidation aluminium formwork to the homogeneous aperture structure that makes is used scanning electron microscope to be characterized, from its result, the anodic oxidation aluminium formwork that the anodic oxidation aluminium formwork of homogeneous aperture structure is vesicular structure, wherein, the clear opening that porous is ordered arrangement, clear opening is the homogeneous aperture structure, and its bore dia is 20～80nm, and the thickness of the anodic oxidation aluminium formwork of homogeneous aperture structure is 2～100 μ m.They are two years old, preparation method's science, effective, both prepared the anodic oxidation aluminium formwork of homogeneous aperture structure, the clear opening that the hole that makes again the anodic oxidation aluminium formwork of the homogeneous aperture structure that makes is ordered arrangement, also owing to only by changing anodised voltage, just having avoided the introducing of mixing acid, reduce complicacy and the cost of preparation, reduced the pollution to environment.
As the further embodiment of beneficial effect, the one, the purity of aluminium flake is preferably >=99.9%, guaranteed the quality of the anodic oxidation aluminium formwork of homogeneous aperture structure.The 2nd, preferably, before aluminium flake is carried out to anodic oxidation, first it alternately is placed in to ethanol and acetone ultrasonic cleaning 2～3 times, then dries after with deionized water, it being cleaned repeatedly, afterwards, being placed on vacuum tightness is 10
-5pa, temperature are the 5h that anneals under 500 ℃, have avoided the introducing of impurity, have guaranteed the purity of the anodic oxidation aluminium formwork of homogeneous aperture structure.The 3rd, the anodizing time in step 1 is preferably 2～6h, the configuration of chromic acid that the phosphoric acid that phosphorus chromic acid mixing solutions is preferably 6wt% by concentration and concentration are 1.5wt% forms, for the anodic oxidation aluminium formwork of the homogeneous aperture structure that obtains high-quality is had laid a good foundation.
The accompanying drawing explanation
Below in conjunction with accompanying drawing, optimal way of the present invention is described in further detail.
Fig. 1 is one of the anodic oxidation aluminium formwork of homogeneous aperture structure that the preparation method is made result of using scanning electron microscope (SEM) to be characterized.Wherein, the SEM image of the anodic oxidation aluminium formwork longitudinal profile that Fig. 1 a is the homogeneous aperture structure, the high magnification SEM image that Fig. 1 b is respective markers in Fig. 1 a; Scale in Fig. 1 a and Fig. 1 b is respectively 5 μ m and 200nm.As seen from Figure 1, the clear opening that the duct in the anodic oxidation aluminium formwork of homogeneous aperture structure is the aperture homogeneous.
Embodiment
At first buy from market or make by ordinary method:
The aluminium flake of purity >=99.9%; Oxalic acid solution; The phosphorus chromic acid mixing solutions that the chromic acid configuration that the phosphoric acid that is 6wt% by concentration and concentration are 1.5wt% forms.
Before aluminium flake is carried out to anodic oxidation, first it alternately is placed in to ethanol and acetone ultrasonic cleaning 2～3 times, then dries after with deionized water, it being cleaned repeatedly; Afterwards, being placed on vacuum tightness is 10
-5pa, temperature are the 5h that anneals under 500 ℃.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.2mol/L, anodic oxidation 6h under the volts DS of 20V.Be placed on again in the phosphorus chromic acid mixing solutions under 58 ℃ and soak 4h, obtain intermediate product.
The concrete steps of preparation are:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.25mol/L, anodic oxidation 5h under the volts DS of 30V.Be placed on again in the phosphorus chromic acid mixing solutions under 59 ℃ and soak 3.8h, obtain intermediate product.
The concrete steps of preparation are:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.3mol/L, anodic oxidation 4h under the volts DS of 40V.Be placed on again in the phosphorus chromic acid mixing solutions under 60 ℃ and soak 3.5h, obtain intermediate product.
Embodiment 4
The concrete steps of preparation are:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.35mol/L, anodic oxidation 3h under the volts DS of 50V.Be placed on again in the phosphorus chromic acid mixing solutions under 61 ℃ and soak 3.3h, obtain intermediate product.
Embodiment 5
The concrete steps of preparation are:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.4mol/L, anodic oxidation 2h under the volts DS of 60V.Be placed on again in the phosphorus chromic acid mixing solutions under 62 ℃ and soak 3h, obtain intermediate product.
Obviously, those skilled in the art can carry out various changes and modification and not break away from the spirit and scope of the present invention to the preparation method of the anodic oxidation aluminium formwork of homogeneous aperture structure of the present invention.Like this, if of the present invention these are revised and within modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention also is intended to comprise these changes and modification interior.
Claims (5)
1. the preparation method of the anodic oxidation aluminium formwork of a homogeneous aperture structure, adopt the two-step anodization method, it is characterized in that completing steps is as follows:
Step 1, first be placed in aluminium flake the oxalic acid solution that concentration is 0.2～0.4mol/L, and under the volts DS of 20～60V, anode is oxidizing to few 2h, then be placed in the phosphorus chromic acid mixing solutions under 58～62 ℃ and soak at least 3h, obtains intermediate product;
Step 2, it is the constant temperature oxalic acid solution that 4～20 ℃, concentration are 0.2～0.4mol/L that intermediate product is placed in to temperature, be that 20～60V, voltage build-up rate are to carry out anodic oxidation under+0.1～25V/h, the final voltage volts DS that is 25～65V in starting voltage, make the anodic oxidation aluminium formwork of homogeneous aperture structure;
20～80nm that the bore dia that the thickness of the anodic oxidation aluminium formwork of described homogeneous aperture structure is 2～100 μ m, clear opening is the homogeneous aperture.
2. the preparation method of the anodic oxidation aluminium formwork of homogeneous aperture structure according to claim 1, the purity that it is characterized in that aluminium flake is >=99.9%.
3. the preparation method of the anodic oxidation aluminium formwork of homogeneous aperture structure according to claim 1, it is characterized in that before aluminium flake is carried out to anodic oxidation, first it alternately is placed in to ethanol and acetone ultrasonic cleaning 2～3 times, after with deionized water, it being cleaned repeatedly again, dry, afterwards, being placed on vacuum tightness is 10
-5pa, temperature are the 5h that anneals under 500 ℃.
4. the preparation method of the anodic oxidation aluminium formwork of homogeneous aperture structure according to claim 1, is characterized in that the anodizing time in step 1 is 2～6h.
5. the preparation method of the anodic oxidation aluminium formwork of homogeneous aperture structure according to claim 1, is characterized in that the chromic acid configuration that phosphoric acid that phosphorus chromic acid mixing solutions is 6wt% by concentration and concentration are 1.5wt% forms.
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| CN201210197115.5A CN103484915A (en) | 2012-06-09 | 2012-06-09 | Preparation method of uniform-aperture anodized aluminum template |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793437A (en) * | 2005-11-23 | 2006-06-28 | 哈尔滨工业大学 | Process for preparing porous anode aluminium oxide mould of height ordered by mixed acid electrolyzing liquid |
| US7125610B2 (en) * | 2003-03-17 | 2006-10-24 | Kemet Electronics Corporation | Capacitor containing aluminum anode foil anodized in low water content glycerine-phosphate electrolyte without a pre-anodizing hydration step |
| 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 |
| CN102127788A (en) * | 2011-01-22 | 2011-07-20 | 青岛大学 | Method for preparing overlarge crystal-cell porous pellumina |
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2012
- 2012-06-09 CN CN201210197115.5A patent/CN103484915A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7125610B2 (en) * | 2003-03-17 | 2006-10-24 | Kemet Electronics Corporation | Capacitor containing aluminum anode foil anodized in low water content glycerine-phosphate electrolyte without a pre-anodizing hydration step |
| CN1793437A (en) * | 2005-11-23 | 2006-06-28 | 哈尔滨工业大学 | Process for preparing porous anode aluminium oxide mould of height ordered by mixed acid electrolyzing liquid |
| 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 |
| CN102127788A (en) * | 2011-01-22 | 2011-07-20 | 青岛大学 | Method for preparing overlarge crystal-cell porous pellumina |
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