CN104947167B - Method for preparing porous anode aluminum oxide nanotemplate with two consistent faces - Google Patents
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Abstract
The invention discloses a method for preparing a porous anode aluminum oxide nanotemplate with two consistent faces, and relates to the material technology. The method comprises the following steps that firstly, an aluminum sheet is polished; secondly, the aluminum sheet serves as an anode, graphite serves as a cathode, and a first-time electrochemical anode hard oxidation reaction is carried out to form a porous oxidation layer; thirdly, an acid mixed solution of CrO3 with the concentration of 0.1mol/L to 0.5mol/L and H3PO4 with the concentration of 0.2mol/L to 0.5mol/L is adopted to remove the porous oxidation layer formed through first-time oxidation; fourthly, the pit-contained aluminum sheet treated in the step three serves as the anode, the graphite serves as the cathode, a second-time electrochemical anode hard oxidation reaction is carried out to obtain the ordered porous anode aluminum oxide nanotemplate; fifthly, the rest of aluminum is removed; and sixthly, a blocking layer is removed, broaching is carried out, and the ordered porous anode aluminum oxide nanotemplate with the two consistent faces is obtained. The method ensures consistency of the positive face and the reverse face of the AAO template and ordering of a nano structure; and the problem that the consistency of the two faces obtained through a one-time anode hard oxidation method is poor is solved.
Description
Technical field
The present invention relates to material technology, more particularly to a kind of preparation method of porous anodic aluminium oxide nano-form.
Background technology
The main component of porous anodic aluminium oxide (AAO) template is Al2O3, it is corresponding with rafifinal (99.999%)
Obtained in acidic electrolysis solution Anodic Oxidation.Wherein metallic aluminium is applying certain external electric field and specific as anode
Under condition of work, the time of reaction is controlled, on the surface of anode aluminium the oxide-film that a layer thickness is tens to hundreds of micron is formed.
Hexagonal periodic structure of the nano-pore arrangement with high-sequential in the alumina formwork for ultimately forming, pitch of holes and aperture can
Accomplish tens to hundreds of nanometer, hole density is about 109～1011/cm2.AAO templates are widely used in and prepare various ordered arrangements
Nano material and device, the spy such as the ratio with preparation process is simple, hole depth and aperture is big, hole density is high, pore size is controllable
Point.In addition filter membrane being alternatively arranged as separating-purifying, as carrier catalytic reaction being used for, as pellicle biomedicine is used for
Field.Also have a wide range of applications in one-dimensional magnetic nano-device (sensor, microwave device etc.) field.
Because ordered porous alumina nano-form is in the extremely important effect of nano science research field, many is caused
The concern of scientist.The preparation method of aluminium oxide nano-form also experienced a very long evolution, initial AAO templates
It is to be prepared using an anodizing, although AAO back sides hole prepared by once oxidation method is presented regularly arranged, but
It is that the positive hole pattern degree of order is very poor.In order to prepare all regular orderly AAO templates of two sides hole, many researchers adopt
Pre-embossed technology pre-formed some regular shallow hole structures on aluminium flake, then carry out again on its basis anodic oxidation and obtain
To the regular consistent AAO templates of two sides hole, such as using SiC templates, optical diffraction gratings, afm scan, poly-
The technologies such as pyrophosphate ion beam, polystyrene are realizing pre-embossed, but method high costs of these outside inductions, complex process.
Nineteen ninety-five, Masuda et al. propose first two-step electrochemical anodizing method (H.Masuda, K.Fukuda, Science 1995), first lead to
Cross an anodic oxidation and generate the regularly arranged nano aperture of presentation hexagon in the self-organizing of aluminum oxide bottom, while in aluminium flake table
Face can also form corresponding pit；Then under 60 DEG C of temperature conditionss, in the H of 6wt%3PO4With the H of 1.8wt%2CrO4It is mixed
Close and remove in solution the oxide layer that once oxidation is formed, finally carry out two-step anodization in the dimpled aluminium base of band again and form rule
The nano aperture structure then arranged.This two-step anodization method that surface pre-embossed is realized using self assembly, is not only dropped
Low production cost, and the AAO template positive and negatives prepared have uniformity and the very high degree of order, therefore extensively adopted
With.
AAO templates prepared by anodic oxidation are typically using acid solutions such as oxalic acid, sulfuric acid and phosphoric acid as electrolyte, wherein
It is the most universal with oxalic acid.In oxalic acid system, the soft method for oxidation for generally adopting now.The voltage for applying is relatively low, only 40～
60V.Because voltage is low, anodic current density is little, therefore the speed of growth in hole is very slow, and only 2-6um/h causes the reaction time
It is very long.Simultaneously soft to aoxidize the size that also limit pitch of holes, pitch of holes can only accomplish the scope of 100～150nm, cause Kong Mi
Degree is larger.When the voltage for applying exceedes the breakdown voltage of electrolyte, oxidation film layer will be burnt by high electrical breakdown.
2006, Woo Lee et al. used oxalic acid as electrolyte, had been prepared using the hard method for oxidation of anode many
Porous aluminum oxide template (W.Lee, R.Ji, U.Gosele, K.Nielsch, Nature materials 2006).It is pre- by low pressure
Oxidation is come the method for improving breakdown voltage and the mode progressively boosted so that voltage brings up to 100～150V.Due to voltage height,
Anodic current density is big, therefore the speed of growth in hole is very fast, can reach 50～70um/h, is the 25～35 of soft oxidation rate
It is big again.The pitch of holes that simultaneously prepared by hard oxidation is bigger, can accomplish 200～300nm, greatly reduces hole density.But it is low
Pressure pre-oxidation and progressively boost process cause the front degree of order of alumina formwork prepared by the hard method for oxidation of anode very low,
The two sides uniformity of hole pattern cannot be ensured.
In sum, at present using oxalic acid as electrolyte, although the AAO templates prepared using the soft oxidizing process of secondary anode
Preferably, but there are some defects, for example：Reaction speed is slow, and long preparation period, while prepared pitch of holes is little, causes hole
Density is too high.Although improving voltage can improve reaction speed and pitch of holes, using the method for soft oxidation, when voltage exceedes
Oxidation film layer is will result in when limiting scope breakdown and damage.Although can significantly be increased using the hard oxidizing process of anode
The speed of growth and pitch of holes of AAO templates, shortens manufacturing cycle, reduces hole density, but hard using a current anode
The aluminium oxide nano-form front degree of order prepared by method for oxidation is very low, it is impossible to ensure hole pattern two sides uniformity.How to exist
Under conditions of hard oxidation, the consistent porous aluminum oxide nano template in two sides is prepared, become difficulties in the urgent need to address.
The present invention can well solve this difficult problem.
The content of the invention
The technical problem to be solved be to provide it is a kind of can quickly prepare hole pattern two sides it is consistent porous sun
The preparation method of pole aluminium oxide nano-form.
The present invention solves the technical scheme of the technical problem employing, the consistent porous anodic aluminium oxide nano-form in two sides
Preparation method, it is characterised in that comprise the steps：
Step one, aluminium flake is processed by shot blasting；
Step 2, using the aluminium flake after polishing as anode, graphite carries out first time Anodic and aoxidizes firmly as negative electrode
Reaction, forms porous oxide coatingses；
The described hard oxidation reaction process of first time Anodic is：Grass with concentration as 0.2mol/L-0.4mol/L
Acid solution is electrolyte, and temperature environment -5～5 DEG C first add 40V 2～10min of voltage response, then with the average speed of 0.5-1V/s
Degree rises high voltage to second voltage value, to reach continue after second voltage value and reacts 10～50min, the scope of the second voltage value
For 100-150V；
Step 3, using the CrO of 0.1-0.5mol/L3With the H of 0.2-0.5mol/L3PO4Acidic mixed solution is removed once
The porous oxide coatingses that oxidation is formed, expose the aluminium flake with regular orderly pit below；
Step 4, step 3 is processed after the dimpled aluminium flake of band as anode, graphite carries out second as negative electrode
The hard oxidation reaction of Anodic, obtains orderly porous anodic aluminium oxide nano-form；
The described hard oxidation reaction process of second Anodic is：Keeping temperature is -5～5 DEG C, electric in 100-150V
Pressure, first reacts 1～5min, then in 10-15min using the oxalic acid solution that concentration is 0.005～0.05mol/L as electrolyte
The interior oxalic acid solution that 0.3～1mol/L is added dropwise in electrolyte with uniform speed so as to which concentration reaches 0.2～0.4mol/L,
10～60min is reacted again；
Step 5, the remaining aluminium of removal；
Step 6, removal barrier layer, then reaming obtains the consistent porous anodic aluminium oxide nanometer mould in orderly two sides
Plate.
Further, the step one is：It is that 99.99% aluminium flake is made conventional high-temperature annealing and cleaned pre- to purity
Process, using pretreated high-purity aluminium flake as anode, graphite, as negative electrode, is 1 in perchloric acid and ethanol volume ratio:4 it is mixed
In closing solution, setting voltage is 20 --- 25V, cell reaction 2min, aluminium flake front is processed by shot blasting.
The step 2 is：Using the aluminium flake after polishing as anode, graphite carries out first time electrochemistry as negative electrode
The hard oxidation reaction of anode：Oxalic acid solution with 0.3mol/L sets reaction temperature as 1 DEG C as electrolyte, first adds 40V voltage responses
5min, then adjusts voltage to 120V with the speed of (0.5-1) V/s, and 30min is then reacted again.
The step 3 is：Using the CrO of 0.2mol/L3With the H of 0.4mol/L3PO4Acidic mixed solution removes an oxygen
Change the porous oxide coatingses for being formed, expose the aluminium flake with regular orderly pit below；
The step 4 is：, used as anode, graphite carries out second electrochemistry to aluminium flake prepared by step 3 as negative electrode
The hard oxidation reaction of anode：Reaction temperature is kept to be 1 DEG C, voltage is 120V, first using the oxalic acid solution of 0.005mol/L as initial
Electrolyte, after reaction 2min, during continuing to react, the oxalic acid solution of 1mol/L is added dropwise in electrolyte, is at the uniform velocity dripped
Plus after 15min, make solution concentration reach 0.3mol/L.Subsequently 30min is reacted again, finally give regular template with nanoholes；
The step 5 is：Nano-form prepared by step 4 is put into into 0.2mol/LCuCl2With 14wt%HCl and go
The unnecessary aluminium in the back side is removed in the mixed solution of ionized water.
The invention has the beneficial effects as follows：Oxidation voltage is brought up to more than 100V by the hard oxidizing process of anode, on the one hand be increased
Reaction speed, highly shortened process cycle, and another aspect high pressure also increases pitch of holes, reaches 200～300nm, reduce
Hole density.Simultaneously the present invention is by way of two-step anodization, it is ensured that the double-edged uniformity of AAO templates and nanometer
The degree of order of structure, solves a difficult problem for the hard oxidizing process two sides uniformity difference of anode.The present invention prepares the consistent AAO in two sides
The method of template is simply efficient, not only significantly shortens the manufacturing cycle of AAO templates, reduces production cost, and in order
Degree is high, significant in the application of the aspect such as nano material preparation and filtering material to promoting it.
Description of the drawings
Fig. 1 is the schematic flow sheet of the present invention.
Fig. 2 is the front SEM figures of the consistent porous aluminum oxide nano template in two sides prepared by the embodiment of the present invention 1；
Fig. 3 is the reverse side SEM figures of the consistent porous aluminum oxide nano template in two sides prepared by the embodiment of the present invention 1；
Fig. 4 is the section SEM figures of the consistent porous aluminum oxide nano template in two sides prepared by the embodiment of the present invention 1.
Specific embodiment
Referring to Fig. 1～4.
Embodiment 1
Step one, first by the aluminium flake that purity is 99.99% cut into the length of side be 30cm square, through conventional high-temperature
Annealing and cleaning pretreatment.Using pretreated high-purity aluminium flake as anode, graphite as negative electrode, in perchloric acid and ethanol
Volume ratio is 1:In 4 mixed solution, setting voltage is 20V, cell reaction 2min, and aluminium flake front is processed by shot blasting.
Step 2, using the aluminium flake after polishing as anode, graphite carries out first time Anodic hard as negative electrode
Oxidation reaction.Oxalic acid solution with 0.3mol/L sets reaction temperature as 1 DEG C as electrolyte, first adds 40V voltage responses 5min,
Then voltage is adjusted to 120V with the speed of (0.5-1) V/s, 30min is then reacted again.
Step 3, using the CrO of 0.2mol/L3With the H of 0.4mol/L3PO4Acidic mixed solution removes once oxidation and is formed
Porous oxide coatingses, expose the aluminium flake with regular orderly pit below；
, used as anode, graphite carries out second Anodic hard as negative electrode for step 4, the aluminium flake for preparing step 3
Oxidation reaction.Reaction temperature is kept to be 1 DEG C, voltage is 120V, first using the oxalic acid solution of 0.005mol/L as initial electrolysis liquid,
After reaction 2min, during continuing to react, the oxalic acid solution of 1mol/L is added dropwise in electrolyte, 15min is at the uniform velocity added dropwise
Afterwards, solution concentration is made to reach 0.3mol/L.Subsequently 30min is reacted again, finally give regular template with nanoholes.
Step 5, by step 4 prepare nano-form be put into 0.2mol/LCuCl2With 14wt%HCl and deionized water
Mixed solution in remove the unnecessary aluminium in the back side.
Step 6, the size (reaming) that barrier layer and adjustment aperture are removed using phosphoric acid.Finally give the bilateral of standard
Porous aluminum oxide nano template, the nano aperture consistent appearance of its positive and negative is 265nm with identical pitch of holes, and aperture is
60nm, hole depth is 46um.
Embodiment 2
Step one, first by the aluminium flake that purity is 99.99% cut into the length of side be 30cm square, through conventional high-temperature
Annealing and cleaning pretreatment.High-purity aluminium flake after using process as anode, graphite as negative electrode, in perchloric acid and ethanol body
Product is than being 1:In 4 mixed solution, setting voltage is 25V, cell reaction 2min, and aluminium flake front is processed by shot blasting.
Step 2, using the aluminium flake after polishing as anode, graphite carries out first time Anodic hard as negative electrode
Oxidation reaction.Oxalic acid solution with 0.3mol/L sets reaction temperature as 1 DEG C as electrolyte, first adds 40V voltage responses 5min,
Then voltage is adjusted to 110V with the speed of (0.5-1) V/s, 30min is then reacted again.
Step 3, using the CrO of 0.2mol/L3With the H of 0.4mol/L3PO4Acidic mixed solution removes once oxidation and is formed
Porous oxide coatingses, expose the aluminium flake with regular orderly pit below；
, used as anode, graphite carries out second Anodic hard as negative electrode for step 4, the aluminium flake for preparing step 3
Oxidation reaction.Reaction temperature is kept to be 1 DEG C, voltage is 110V, first using the oxalic acid solution of 0.005mol/L as initial electrolysis liquid,
After reaction 1min, during continuing to react, the oxalic acid solution of 1mol/L is added dropwise in electrolyte, 15min is at the uniform velocity added dropwise
Afterwards, solution concentration is made to reach 0.3mol/L.Subsequently 20min is reacted again, finally give regular template with nanoholes.
Step 5, by step 4 prepare nano-form be put into 0.2mol/LCuCl2With 14wt%HCl and deionized water
Mixed solution in remove the unnecessary aluminium in the back side.
Step 6, the size that barrier layer and adjustment aperture are removed using phosphoric acid.Finally give the bilateral porous oxygen of standard
Change aluminium nano-form, the nano aperture consistent appearance of its positive and negative is 225nm with identical pitch of holes, and aperture is 60nm, hole
Depth is 40um.
Claims (4)
1. the preparation method of the consistent porous anodic aluminium oxide nano-form in two sides, it is characterised in that comprise the steps：
Step one, aluminium flake is processed by shot blasting；
Step 2, using the aluminium flake after polishing as anode, graphite carries out the firmly oxidation of first time Anodic anti-as negative electrode
Should, form porous oxide coatingses；
The described hard oxidation reaction process of first time Anodic is：Oxalic acid with concentration as 0.2mol/L-0.4mol/L is molten
Liquid is electrolyte, and temperature environment -5～5 DEG C first add 40V 2～10min of voltage response, then with the average speed liter of 0.5-1V/s
High voltage to reach continue after second voltage value and react 10～50min to second voltage value, and the scope of the second voltage value is
100-150V；
Step 3, using the CrO of 0.1-0.5mol/L3With the H of 0.2-0.5mol/L3PO4Acidic mixed solution removes once oxidation
The porous oxide coatingses of formation, expose the aluminium flake with regular orderly pit below；
Step 4, step 3 is processed after the dimpled aluminium flake of band as anode, graphite as negative electrode, carry out second it is electrochemical
The hard oxidation reaction of anode is learned, orderly porous anodic aluminium oxide nano-form is obtained；
The described hard oxidation reaction process of second Anodic is：Keeping temperature is -5～5 DEG C, in 100-150V voltages
Under, first 1～5min is reacted as electrolyte using the oxalic acid solution that concentration is 0.005～0.05mol/L, then in 10-15min
The oxalic acid solution of 0.3～1mol/L is added dropwise in electrolyte with uniform speed so as to which concentration reaches 0.2～0.4mol/L, then
10～60min of reaction；
Step 5, the remaining aluminium of removal；
Step 6, removal barrier layer, then reaming obtains the consistent porous anodic aluminium oxide nano-form in orderly two sides.
2. the preparation method of the consistent porous anodic aluminium oxide nano-form in two sides as claimed in claim 1, it is characterised in that institute
Stating step one is：Be to purity 99.99% aluminium flake make conventional high-temperature annealing and clean pretreatment, by pretreated height
Fine aluminium piece, as negative electrode, is 1 in perchloric acid and ethanol volume ratio as anode, graphite:In 4 mixed solution, setting voltage is
20-25V, cell reaction 2min, are processed by shot blasting to aluminium flake front.
3. the preparation method of the consistent porous anodic aluminium oxide nano-form in two sides as claimed in claim 1, it is characterised in that institute
Stating step 2 is：
Using the aluminium flake after polishing as anode, graphite carries out the hard oxidation reaction of first time Anodic as negative electrode：With
The oxalic acid solution of 0.3mol/L is electrolyte, sets reaction temperature as 1 DEG C, first adds 40V voltage responses 5min, then with (0.5-
1) speed of V/s adjusts voltage to 120V, and 30min is then reacted again.
4. the preparation method of the consistent porous anodic aluminium oxide nano-form in two sides as claimed in claim 3, it is characterised in that institute
Stating step 3 is：Using the CrO of 0.2mol/L3With the H of 0.4mol/L3PO4Acidic mixed solution removes many of once oxidation formation
Hole oxide layer, exposes the aluminium flake with regular orderly pit below；
The step 4 is：, used as anode, graphite carries out second Anodic to aluminium flake prepared by step 3 as negative electrode
Hard oxidation reaction：Reaction temperature is kept to be 1 DEG C, voltage is 120V, first using the oxalic acid solution of 0.005mol/L as initial electrolysis
Liquid, after reaction 2min, during continuing to react, the oxalic acid solution of 1mol/L is added dropwise in electrolyte, is at the uniform velocity added dropwise
After 15min, solution concentration is set to reach 0.3mol/L.Subsequently 30min is reacted again, finally give regular template with nanoholes；
The step 5 is：Nano-form prepared by step 4 is put into into 0.2mol/LCuCl2With 14wt%HCl and deionization
The unnecessary aluminium in the back side is removed in the mixed solution of water.
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| EP3431637A1 (en) | 2017-07-18 | 2019-01-23 | IMEC vzw | Porous solid materials and methods for fabrication |
| CN110042448B (en) * | 2019-04-30 | 2021-04-30 | 铜仁学院 | Preparation method of porous anodic aluminum oxide template |
| CN110417297B (en) * | 2019-07-30 | 2020-10-20 | 北京航空航天大学 | Porphyrin/aluminum oxide nano-channel film and application thereof in energy conversion device |
| CN110993864A (en) * | 2019-11-21 | 2020-04-10 | 四川新敏雅电池科技有限公司 | Battery separator, method for manufacturing same, and lithium ion battery |
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| EP1884578A1 (en) * | 2006-07-31 | 2008-02-06 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | A method of manufacturing a self-ordered porous structure of aluminium oxide, a nanoporous article and a nano object |
| CN102953108A (en) * | 2011-08-27 | 2013-03-06 | 沈阳黎明航空发动机(集团)有限责任公司 | Technology for automatically controlling hard anodic oxidation |
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| EP1884578A1 (en) * | 2006-07-31 | 2008-02-06 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | A method of manufacturing a self-ordered porous structure of aluminium oxide, a nanoporous article and a nano object |
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