CN102864476B - Preparation method of through-hole anodic aluminum oxide template - Google Patents
Preparation method of through-hole anodic aluminum oxide template Download PDFInfo
- Publication number
- CN102864476B CN102864476B CN201210375745.7A CN201210375745A CN102864476B CN 102864476 B CN102864476 B CN 102864476B CN 201210375745 A CN201210375745 A CN 201210375745A CN 102864476 B CN102864476 B CN 102864476B
- Authority
- CN
- China
- Prior art keywords
- hole
- preparation
- aluminum oxide
- anodic
- anodic oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
- Cold Cathode And The Manufacture (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a preparation method directly producing a barrier-free through-hole anodic aluminum oxide template during anodizing. According to extensibility of metallic aluminum and the diffusion principle of intermetallic interface, double aluminum foil layers are laminated by pressurizing. The first aluminum foil layer is completely oxidized by single-side anodizing and reaches the second aluminum foil layer, so that a fully through-hole first porous anodic aluminum oxide film. The aluminum oxide template with 100% through holes can be obtained by the preparation method, and the need of using complex post-treatment process to remove a barrier layer is avoided. Through-hole time points can be precisely positioned according to anodizing curves. The thickness of the through-hole aluminum oxide template can be controlled by regulating thickness of the first aluminum foil layer or by double anodizing. The preparation method is applicable to the process of mild anodizing and high-field anodizing of aluminum foils in various aqueous electrolytes.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate to a kind of preparation method of porous anodic alumina template of through hole, be specifically related to a kind of without the need to special aftertreatment, by means of only one side anodic oxidation two-layer compound aluminium foil, thus the simple and easy electrochemical preparation method of through-hole anodic aluminum oxide template not with blocking layer.
Background technology
Porous anodic aluminium oxide (PAA) is that a class is obtained by electrochemical anodic oxidation in suitable electrolytic solution, have regular pore canal arrangement and cellular is the closely packed porous material of six prisms.PAA is as nano-template material, there is the features such as preparation technology is simple, hole density is high, length-to-diameter ratio is large, duct arranging rule, pore size are controlled, be widely used in the preparation of low-dimensional nano structure of metal, alloy, nonmetal, the various types of materials such as nonmetal oxide, polymkeric substance, all have broad application prospects in various fields such as nonlinear optics, nano-electron, electrochemistry.
With regard to the application of PAA template, in most cases need through-hole template.But owing to there is the alumina barrier layer of one deck densification bottom the porous layer of PAA film, the PAA template of wishing to get through hole must manage to remove this layer of blocking layer.At present, the universal method preparing through hole PAA template is: first adopt CuCl
2, HgCl
2or SnCl
4aluminum substrate corrosion dissolution bottom the PAA film prepared falls by solution, obtains pure PAA film; Be immersed in again in phosphoric acid solution, removed the blocking layer of PAA film by chemical corrosion method, finally obtain the PAA template of through hole.But this method is in the process removing aluminum substrate, and inevitably bring some beavy metal impurities in nano aperture, this may bring restriction to the application of template.In addition, it is uncontrollable that phosphoric acid solution removes the chemical corrosion process on blocking layer, and PAA film is immersed in duct in phosphoric acid solution is also corroded, and reaming in various degree can occur the through hole PAA template that therefore this legal system is standby.The another kind of method removing PAA film blocking layer is so-called step-decreasing voltage method: according to barrier layer thickness and the proportional principle of voltage, by progressively reducing anodic oxidation voltage, make blocking layer progressively thinning, until through hole.Furneaux etc. report the earliest by step-decreasing voltage method, make the PAA film through hole (Furneaux, et al. Nature, 1989,337:147) prepared in phosphoric acid solution.But the processing parameters such as the method necessary strict controlled hypotension amplitude, electrolyte temperature, whole pressure reduction is very complicated, consuming time longer, and is difficult to ensure to bore a hole in blocking layer 100%.Therefore, in most cases, still need again by phosphoric acid solution immersion treatment to obtain the PAA template of complete through hole.
Preparation PAA through-hole template also has a kind of easier electrochemical method: in perchloric acid/methyl alcohol mixed liquor, take print as anode, big area aluminium flake is negative electrode, be energized very short time at a dc voltage, the through hole PAA template (Yuan of larger area can be obtained, et al. Chem. Mater., 2004,16:1841).But this method all has requirement to PAA thicknesses of layers and character, and side, PAA film blocking layer bore size is difficult to control, and operation easier is very large, and electrolytic solution not environmentally, may destroy to some extent by the appearance and size of fenestra.
In sum, prepare at present the method for PAA through-hole template, there is various defect, as: beavy metal impurity pollutes, remove blocking layer complex process, length consuming time, bore size are difficult to control and electrolytic solution not environmentally etc.Therefore, prepare PAA through-hole template with finding a kind of simple and effective, and do not destroy inherent structure and the size of film, be applicable to the method for different thickness PAA film simultaneously, become difficulties in the urgent need to address.
Summary of the invention
The object of the present invention is to provide one not need special aftertreatment, in anode oxidation process, directly prepare the method for through hole PAA template.
The technical solution realizing the object of the invention is: a kind of preparation method of through-hole anodic aluminum oxide template, comprises the following steps:
The Natural Oxide Film on step 1, removal high-purity aluminum foil surface;
Step 2, carry out pressurization compound to the two panels high-purity aluminum foil be stacked, moulding pressure is 5-10 MPa, and the dwell time is 30-60 min;
Step 3, one side anodic oxidation is carried out to the high-purity aluminum foil of compound;
Step 4, after sudden change appears in the voltage on anodic oxidation curve, then anodised for constant current electric current to be reduced by half, or after sudden change appears in the electric current on anodic oxidation curve, then maintain constant voltage anodised voltage constant, then terminate after continuing to be oxidized half an hour;
Step 5, last, the PAA template of complete through hole is namely obtained by mechanically peel.
Removal Natural Oxide Film described in step 1 is in the sodium hydroxide solution of 2wt % aluminium foil being immersed 70 DEG C 2 minutes.
Pressurization described in step 2 adopts oil press.
The suitable depth of the clad aluminum foil of the coverlet surface anode oxidation described in step 3 is 20-150 μm.
One side anodic oxidation described in step 3 can adopt gentle anodic oxidation or High-Field anodic oxidation.
One side anodic oxidation described in step 3 can adopt an anodic oxidation or two-step anodization.
The present invention compared with prior art, its remarkable advantage:
(1) the first layer aluminium foil complete oxidation after being transitioned into second layer aluminium foil, blocking layer is transferred to second layer aluminium foil thereupon, by mechanically peel, makes the first layer PAA film depart from, directly obtains the PAA template of through hole state, without the need to considering the removal problem on blocking layer.
(2) owing to not needing the removal problem considering PAA film blocking layer, therefore prepare the time of through hole PAA template just by anodised Time dependent, preparation efficiency significantly improves.
(3) owing to not needing the removal problem considering PAA film blocking layer, therefore after having prepared, the duct of gained PAA template is completely the same with state during preparation, there is not the problem such as reaming, excessive corrosion, thus realizes the accurate control of PAA templating nanoparticles pore size.
(4) by regulating the thickness of the first layer aluminium foil, or adopting two-step anodization method, the PAA through-hole template that thickness changes in a big way can be prepared.
(5) by observing the change state of PAA film preparation anodic oxygenation parameters, semi-quantitatively can determine the through hole state of PAA film, thus understand through hole degree in time and control the through hole time, avoid the etching process on the removal blocking layer of pure empirical formula.
(6) because through hole PAA template is that a step directly obtains, and be not connected with aluminum substrate, therefore without the need to chemical reagent process aluminum substrate, save resource, avoid PAA template simultaneously and pollute and environmental pollution, be conducive to suitability for industrialized production.
(7) adopt method of the present invention to prepare in system at sulfuric acid, oxalic acid and tricresyl phosphate class PAA all can adopt, and be applicable to gentle anodic oxidation and High-Field anodic oxidation simultaneously, be also applicable to two-step anodization in addition.
Accompanying drawing explanation
Fig. 1 is the one side constant current anodic oxidation graphic representation of the embodiment of the present invention 1 composite double layer aluminium foil.
Fig. 2 is the scanning electron microscope (SEM) photograph (a is that the bottom surface SEM of PAA through-hole template schemes, and b is be that the section of PAA through-hole template is schemed near the SEM of bottom section) of PAA through-hole template prepared by embodiment 1.
Fig. 3 is the metaloscope figure of PAA through-hole template section prepared by embodiment 3.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Principle of the present invention is as follows: adopt pressurization composite double layer aluminium foil, by one side anode oxidation process, make the first layer aluminium foil (i.e. the aluminium foil of coverlet surface anode oxidation) complete oxidation, and be transitioned into second layer aluminium foil, thus obtain the first layer porous anodic alumina films of complete through hole.Aluminium is the splendid metal of a kind of ductility, and after being fitted by two panels aluminium foil, under external force, the interface of two-layer aluminium foil extruding occurs and extends, and microcosmic produces the physical processes such as mutual anchor chain, embedding, thus makes two-layer aluminium foil compound; Along with continuing of External Force Acting, the two-layer aluminium foil interface of compound, atom each other starts phase mutual diffusion, interface starts to thicken, through namely defining the transitional region of an atomic diffusion mixing after a period of time, because the interaction between atoms metal is far above pure physical action, the force strength therefore between two-layer aluminium foil increases further, this ensures anode oxidation process and can transit to second layer aluminium foil from the first layer aluminium foil.Because this invention adopts the anodised mode of one side, aluminium foil oxidation has directivity, is namely oxidizing to the second layer from the first layer.In the oxidation starting stage, be as good as with traditional single piece aluminum foil anode oxidation process.But when having arrived close to two-layer aluminium foil juncture area, thickness due to individual layer aluminium foil entirety is uneven on microcosmic, simultaneously in anode oxidation process, the distribution of electric field also can difference to some extent, so some position must be caused to take the lead in transitting to the anodic oxidation of second layer aluminium foil.Because transitional region Atomic Arrangement is in state of disarray, therefore interatomic force will be weaker than aluminium foil body, when two-layer aluminium foil interface transitional region is fully anodised and continues the body being oxidized second layer aluminium foil, because alumilite process process volumetric expansion can occur, interface stress is increased sharply, cause the PAA film in this region to rupture in interfaces transition zone position, thus obtain the film of through hole.And after fracture generation, electrolytic solution rapid osmotic zone of fracture, arrives the metallic aluminum that breaking part exposes, now antianode oxygenation parameters produces considerable influence, therefore by observing the change of altering anodization parameters, can determine the time point that fracture starts.Namely after sudden change appears in the voltage on anodic oxidation curve, then anodised for constant current electric current is reduced by half, or after sudden change appears in the electric current on anodic oxidation curve, then maintain the anodised voltage of constant voltage constant, be transitioned into the second layer completely in order to ensure anodic oxidation, then terminate after continuing to be oxidized half an hour.
The present invention is realized by following steps: adopt high-purity aluminum foil, first to be immersed by two panels aluminium foil in the sodium hydroxide solution of the 2wt % of 70 DEG C 2 minutes, removes the Natural Oxide Film on its surface.Again by the laminating of two panels aluminium foil overlap, be fixed in mould, and reserved one section of aluminium foil be separated from each other is outside mould, then mould is put into oil press, operating pressure is 5-10 MPa, and the dwell time is 30-60 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, using the first layer aluminium foil side as anode, then using platinum guaze as negative electrode, carry out one side anodic oxidation.The suitable depth scope of the first layer aluminium foil is 20-150 μm.Electrolytic solution can adopt sulfuric acid, oxalic acid or phosphorus aqueous acid, and electric source modes can adopt constant voltage or constant current, and anodic oxidation type can be gentle anodic oxidation or High-Field anodic oxidation.The real time measure anodic oxidation curve, when altering anodization parameters generation considerable change, reduces to original half (for constant current anodic oxidation) or ME for maintenance constant (for constant voltage anodic oxidation) and maintains half an hour by electric current.Then stop anodic oxidation, the region incision never bonded with blade, makes double-layer aluminum-foil be separated, finally obtains through hole PAA template.
The present invention is further illustrated below by embodiment.
Embodiment 1
First get the aluminum foil strip of two purity 99.99%, length 70 mm, width 20 mm, thickness 150 μm, put into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 10 MPa, and maintain 30 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with 50 mAcm
-2current density (High-Field anodic oxidation), in steady temperature 20
°under C, carry out one side constant current anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure voltage, and occur being reduced by half by electric current when rising fast at voltage, and stop after maintaining 30 min, concrete test curve is shown in Fig. 1.The microscopic appearance of gained sample as shown in Figure 2.Fig. 2 (a) is that the bottom surface SEM after obtained PAA through-hole template and the complete anodic oxidation of the first layer aluminium foil schemes, and bottom the template of through hole completely that can be observed regular arrangement, the average pitch of holes of PAA film nano pore is about 120 nm.Fig. 2 (b) is that the section of the first layer pellumina is schemed near the SEM of bottom section, can find out the straight and complete through hole in duct.By the metaloscope photo of sample section, the thickness about 211.46 μm of PAA through-hole template can be recorded.
Embodiment 2
First get the aluminum foil strip of two purity 99.99%, length 70 mm, width 20 mm, thickness 150 μm, put into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 5 MPa, and maintain 60 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with 50 mAcm
-2current density, in steady temperature 20
°under C, carry out one side constant current anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure voltage, occurs being reduced by half by electric current when rising fast, and stop after maintaining 30 min at voltage.The average pitch of holes of PAA film nano pore is about 117 nm, the thickness of PAA through-hole template about 218.25 μm.
Embodiment 3
First get purity 99.99%, length 70 mm, width 20 mm, thickness is respectively each one of the aluminum foil strip of 150 μm and 100 μm, puts into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 10 MPa, and maintain 30 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, using the aluminium foil side of thickness 100 μm as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with 50 mAcm
-2current density, in steady temperature 20
°under C, carry out one side constant current anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure voltage, occurs being reduced by half by electric current when rising fast, and stop after maintaining 30 min at voltage.Fig. 3 is the metaloscope photo of this sample section, known by scheming, the thickness of PAA through-hole template about 111.59 μm.
Embodiment 4
First get purity 99.99%, length 70 mm, width 20 mm, thickness is respectively each one of the aluminum foil strip of 150 μm and 50 μm, puts into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 7.5 MPa, and maintain 45 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, using the aluminium foil side of thickness 50 μm as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with 50 mAcm
-2current density, in steady temperature 20
°under C, carry out one side constant current anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure voltage, occurs being reduced by half by electric current when rising fast, and stop after maintaining 30 min at voltage.Record the thickness about 60.38 μm of PAA through-hole template.
Embodiment 5
First get the aluminum foil strip of two purity 99.99%, length 70 mm, width 20 mm, thickness 150 μm, put into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 10 MPa, and maintain 30 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with 50 mAcm
-2current density, in steady temperature 20
°under C, carry out one side constant current first time anodic oxidation.After reaction 1 h, stop anodic oxidation, guarantee the non-complete oxidation of the first layer aluminium foil, sample is put into the 1.8 wt% HCrO of 60 ° of C
4with 6 wt% H
3pO
410 h are soaked, to remove first time oxide film in mixed solution.Again with this sample for anode, with first time anodised condition carry out second time anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure voltage, occurs being reduced by half by electric current when rising fast, and stop after maintaining 30 min at voltage.Record the thickness about 20.32 μm of PAA through-hole template.
Embodiment 6
First get purity 99.99%, length 70 mm, width 20 mm, thickness is respectively each one of the aluminum foil strip of 150 μm and 50 μm, puts into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 7.5 MPa, and maintain 45 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, using the aluminium foil side of thickness 50 μm as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with the voltage of 80 V (High-Field anodic oxidation), in steady temperature 20
°under C, carry out the anodic oxidation of one side constant voltage.Oxidization time is determined by the changing conditions of the real time measure electric current, and after electric current downtrending is progressively accelerated, sustaining voltage is constant and stop after maintaining 30 min.The average pitch of holes recording PAA film nano pore is about 152 nm, the thickness of PAA through-hole template about 54.23 μm.
Embodiment 7
First get the aluminum foil strip of two purity 99.99%, length 70 mm, width 20 mm, thickness 150 μm, put into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 10 MPa, and maintain 30 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, as anodised anode, then using platinum guaze as negative electrode.With the sulphuric acid soln of 6 M for electrolytic solution, with 50 mAcm
-2current density (High-Field anodic oxidation), in steady temperature 20
°under C, carry out one side constant current anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure voltage, occurs being reduced by half by electric current when rising fast, and stop after maintaining 30 min at voltage.The average pitch of holes recording PAA film nano pore is about 47 nm, the thickness of PAA through-hole template about 187 μm.
Embodiment 8
First get purity 99.99%, length 70 mm, width 20 mm, thickness is respectively each one of the aluminum foil strip of 150 μm and 50 μm, puts into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 7.5 MPa, and maintain 45 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, using the aluminium foil side of thickness 50 μm as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.3 M for electrolytic solution, with the voltage of 40 V (gentle anodic oxidation), in steady temperature 10
°under C, carry out the anodic oxidation of one side constant voltage.After reaction 8 h, stop anodic oxidation, sample is put into the 1.8 wt% HCrO of 60 ° of C
4with 6 wt% H
3pO
48 h are soaked, to remove the oxide film that first time anodizing generates in mixed solution.Again with this sample for anode, with first time anodised condition carry out second time anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure electric current, and after electric current downtrending is progressively accelerated, sustaining voltage is constant and stop after maintaining 30 min.The average pitch of holes recording PAA film nano pore is about 92 nm, the thickness of PAA through-hole template about 13 μm.
Embodiment 9
First get purity 99.99%, length 70 mm, width 20 mm, thickness is respectively each one of the aluminum foil strip of 150 μm and 20 μm, puts into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 10 MPa, and maintain 30 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, using the aluminium foil side of thickness 20 μm as anodised anode, then using platinum guaze as negative electrode.With the sulphuric acid soln of 0.3 M for electrolytic solution, with the voltage of 25 V (gentle anodic oxidation), in steady temperature 0
°under C, carry out the anodic oxidation of one side constant voltage.After reaction 5 h, stop anodic oxidation, sample is put into the 1.8 wt% HCrO of 60 ° of C
4with 6 wt% H
3pO
44 h are soaked, to remove the oxide film that first time anodizing generates in mixed solution.Again with this sample for anode, with the sulphuric acid soln of 0.3 M for electrolytic solution, with first time anodised condition carry out second time anodic oxidation.Oxidization time is determined by the changing conditions of the real time measure electric current, and after electric current downtrending is progressively accelerated, sustaining voltage is constant and stop after maintaining 30 min.Record the thickness about 7.57 μm of PAA through-hole template.
Embodiment 10
First get the aluminum foil strip of two purity 99.99%, length 70 mm, width 20 mm, thickness 150 μm, put into 2 wt%, 70 simultaneously
°2 min are soaked, to remove the Natural Oxide Film of aluminium foil surface in the NaOH solution of C.By the laminating of two aluminium foil overlaps, and be fixed in mould, then mould is put into oil press, pressurize 7.5 MPa, and maintain 45 min.Take out the two-layer compound aluminium foil bonded subsequently, repeatedly rinse well with deionized water, as anodised anode, then using platinum guaze as negative electrode.With the oxalic acid solution of 0.75 M for electrolytic solution, with 50 mAcm
-2current density, in steady temperature 20
°under C, carry out one side constant current anodic oxidation.After reaction 1 h, stop anodic oxidation, guarantee the non-complete oxidation of the first layer aluminium foil, sample is put into the 1.8 wt% HCrO of 60 ° of C
4with 6 wt% H
3pO
410 h are soaked, to remove once oxidation film in mixed solution.Again with this sample for anode, with the phosphoric acid solution of 0.5 M for electrolytic solution, with the voltage of 60 V, in steady temperature 20
°under C, carry out the anodic oxidation of one side constant voltage second time.Oxidization time is determined by the changing conditions of the real time measure electric current, and after electric current downtrending is progressively accelerated, sustaining voltage is constant and stop after maintaining 30 min.Because experiment applied voltage is far below self-organization voltage 195 V of PAA film in phosphoric acid solution, therefore obtain the PAA template of spination nano pore structure.Record the thickness about 10.58 μm of PAA through-hole template.
Claims (8)
1. a preparation method for through-hole anodic aluminum oxide template, is characterized in that said method comprising the steps of:
The Natural Oxide Film on step 1, removal high-purity aluminum foil surface;
Step 2, carry out pressurization compound to the two panels high-purity aluminum foil be stacked, moulding pressure is 5-10 MPa, and the dwell time is 30-60 min;
Step 3, one side anodic oxidation is carried out to the high-purity aluminum foil of compound;
Step 4, after sudden change appears in the voltage on anodic oxidation curve, then anodised for constant current electric current to be reduced by half, or after sudden change appears in the electric current on anodic oxidation curve, then maintain constant voltage anodised voltage constant, then terminate after continuing to be oxidized half an hour;
Step 5, last, the PAA template of complete through hole is namely obtained by mechanically peel.
2. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the removal Natural Oxide Film described in step 1 is in the sodium hydroxide solution of 2wt % aluminium foil being immersed 70 DEG C 2 minutes.
3. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the pressurization described in step 2 adopts oil press.
4. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the thickness of the clad aluminum foil of the coverlet surface anode oxidation described in step 3 is 20-150 μm.
5. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the anode oxidation process described in step 3 adopts constant current oxidation pattern or constant voltage oxidation model.
6. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that using clad aluminum foil as anode in the one side anodic oxidation described in step 3, using platinum guaze as negative electrode; Electrolytic solution used comprises sulfuric acid, oxalic acid or phosphorus aqueous acid.
7. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the one side anodic oxidation described in step 3 adopts gentle anodic oxidation or High-Field anodic oxidation.
8. the preparation method of through-hole anodic aluminum oxide template according to claim 1, is characterized in that the one side anodic oxidation described in step 3 adopts an anodic oxidation or two-step anodization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210375745.7A CN102864476B (en) | 2012-09-29 | 2012-09-29 | Preparation method of through-hole anodic aluminum oxide template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210375745.7A CN102864476B (en) | 2012-09-29 | 2012-09-29 | Preparation method of through-hole anodic aluminum oxide template |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102864476A CN102864476A (en) | 2013-01-09 |
| CN102864476B true CN102864476B (en) | 2014-12-24 |
Family
ID=47443597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210375745.7A Expired - Fee Related CN102864476B (en) | 2012-09-29 | 2012-09-29 | Preparation method of through-hole anodic aluminum oxide template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102864476B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014130453A1 (en) * | 2013-02-19 | 2014-08-28 | Alumiplate, Inc. | Methods for improving adhesion of aluminum films |
| CN104278308A (en) * | 2013-07-10 | 2015-01-14 | 中国科学院大连化学物理研究所 | Preparation method of though hole anode aluminum oxide |
| CN104726846B (en) * | 2015-03-06 | 2017-03-29 | 西安电子科技大学 | Large-area graphene preparation method based on the orderly copper nano-wire catalysis of high density |
| CN105586649B (en) * | 2016-03-16 | 2017-11-10 | 武汉纺织大学 | A kind of preparation method of low-melting-point metal nanofiber |
| CN106252071B (en) * | 2016-08-05 | 2018-04-03 | 南京理工大学 | A kind of height ratio capacity nanometer dielectric capacitor and preparation method thereof |
| CN108251877A (en) * | 2016-12-29 | 2018-07-06 | 北京有色金属研究总院 | A kind of Woelm Alumina film layer and preparation method thereof |
| JP7183395B2 (en) * | 2019-03-29 | 2022-12-05 | 富士フイルム株式会社 | Aluminum foil, method for producing aluminum foil, current collector, lithium ion capacitor, and lithium ion battery |
| CN110777417A (en) * | 2019-11-21 | 2020-02-11 | 广东风华高新科技股份有限公司 | Hexagonal prism hole type aluminum electrolysis anode corrosion foil and production method thereof |
| CN111733443B (en) * | 2020-05-22 | 2021-07-16 | 东莞东阳光科研发有限公司 | Method for manufacturing electrode foil for aluminum electrolytic capacitor and electrode foil |
| US11583810B2 (en) | 2020-12-14 | 2023-02-21 | Industrial Technology Research Institute | Porous substrate structure and manufacturing method thereof |
| CN114369402B (en) * | 2021-12-18 | 2022-10-11 | 佛山市顺德区固得丽涂料有限公司 | Aluminum alloy coating material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101602A (en) * | 1993-10-09 | 1995-04-19 | 李儒臣 | Super low sulfur graphite and metal composite reinforced gasket material and its making method |
| CN2222608Y (en) * | 1995-09-18 | 1996-03-20 | 王中一 | Device for production of compound honeycomb board |
| WO2003046265A2 (en) * | 2001-11-26 | 2003-06-05 | Massachusetts Institute Of Technology | Thick porous anodic alumina films and nanowire arrays grown on a solid substrate |
| 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 |
| CN101139730A (en) * | 2007-06-12 | 2008-03-12 | 太原理工大学 | Strong anodic oxidation method for preparing porous pellumina |
| CN101629927A (en) * | 2009-08-13 | 2010-01-20 | 上海交通大学 | Porous aluminum oxide film humidity-dependent sensor preparation method |
| CN101654799A (en) * | 2009-09-15 | 2010-02-24 | 江苏工业学院 | Method for preparing highly ordered porous anodic alumina films in superhigh speed |
-
2012
- 2012-09-29 CN CN201210375745.7A patent/CN102864476B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101602A (en) * | 1993-10-09 | 1995-04-19 | 李儒臣 | Super low sulfur graphite and metal composite reinforced gasket material and its making method |
| CN2222608Y (en) * | 1995-09-18 | 1996-03-20 | 王中一 | Device for production of compound honeycomb board |
| WO2003046265A2 (en) * | 2001-11-26 | 2003-06-05 | Massachusetts Institute Of Technology | Thick porous anodic alumina films and nanowire arrays grown on a solid substrate |
| 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 |
| CN101139730A (en) * | 2007-06-12 | 2008-03-12 | 太原理工大学 | Strong anodic oxidation method for preparing porous pellumina |
| CN101629927A (en) * | 2009-08-13 | 2010-01-20 | 上海交通大学 | Porous aluminum oxide film humidity-dependent sensor preparation method |
| CN101654799A (en) * | 2009-09-15 | 2010-02-24 | 江苏工业学院 | Method for preparing highly ordered porous anodic alumina films in superhigh speed |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102864476A (en) | 2013-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102864476B (en) | Preparation method of through-hole anodic aluminum oxide template | |
| CN101962792B (en) | Method for preparing pore diameter controllable through hole anodized aluminum oxide film | |
| US6839219B2 (en) | Laminate for forming capacitor layer and method for manufacturing the same | |
| CN100432301C (en) | Process for preparing porous anode aluminium oxide mould of height ordered by mixed acid electrolyzing liquid | |
| Zhu et al. | The study on oxygen bubbles of anodic alumina based on high purity aluminum | |
| CN101831682A (en) | Method for preparing highly ordered aluminum oxide template by asymmetric two-step anodization | |
| CN101651046B (en) | Preparation method of Al2O3/TiO2 compound dielectric film aluminum electrode foil | |
| CN1995480B (en) | Preparation process for obtaining highly ordered alumina mold | |
| JP6087357B2 (en) | Alumina through-hole membrane and manufacturing method thereof | |
| CN100537851C (en) | Magnesium, aluminium alloy electrolytic solution for differential arc oxidization surface treatment in aluminates system | |
| Zhang et al. | Growth of anodic TiO2 nanotubes in mixed electrolytes and novel method to extend nanotube diameter | |
| CN106065488B (en) | A method of preparing anode aluminium foil using positive negative pulse stuffing anodizing | |
| CN112899754A (en) | Electrolyte for preparing self-sealing hole micro-arc oxidation coating on surface of magnesium alloy and preparation method of coating | |
| WO2012088700A1 (en) | Manufacturing method for anode foil of aluminum electrolytic capacitor | |
| CN104131326B (en) | A kind of electrolyte for magnesium alloy differential arc oxidation | |
| Chen et al. | Morphology evolution of TiO2 nanotubes by a slow anodization in mixed electrolytes | |
| CN104911664B (en) | A kind of method for reducing silumin differential arc oxidation specific energy consumption | |
| Yu et al. | Morphology evolution of porous anodic alumina in mixed H3PO4/NH4F electrolytes | |
| CN101603193A (en) | A kind of method of peeling anodic aluminum oxide film | |
| WO2011099260A1 (en) | Electrode foil, process for producing same, and capacitor using electrode foil | |
| CN102888642A (en) | Preparation method of large-area high-order porous anodised aluminium film | |
| CN103233259B (en) | The oxidation processing technique of CTP plate | |
| CN1995479A (en) | Preparation method of alumina mold with bore diameter more than 500nm | |
| RU2545887C2 (en) | Method of production of flexible nanoporous composite membrane with cellular structure of anode metal oxide or alloy | |
| CN102206847A (en) | Microarc oxidation/sol-gel compound treatment process for magnesium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20160929 |