CN1330794C - Preparation for self-supporting ordered through hole alumina film - Google Patents
Preparation for self-supporting ordered through hole alumina film Download PDFInfo
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- CN1330794C CN1330794C CNB2004100649210A CN200410064921A CN1330794C CN 1330794 C CN1330794 C CN 1330794C CN B2004100649210 A CNB2004100649210 A CN B2004100649210A CN 200410064921 A CN200410064921 A CN 200410064921A CN 1330794 C CN1330794 C CN 1330794C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- 239000004411 aluminium Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- 210000002421 cell wall Anatomy 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 8
- 229940024548 aluminum oxide Drugs 0.000 abstract 5
- 239000002253 acid Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The present invention relates to a preparation method of a self-supporting ordered through-hole aluminum-oxide film, which comprises the following steps: (1) an aluminum piece with a smooth surface is directly defatted, oxide is removed, and the aluminum piece is pretreated; (2) the pretreated aluminum piece is used as an anode, a clean aluminum piece is used as a cathode, an electrolyzing process for the first time is carried out in acidity dielectric solution, electrolyzing time is from 0.5 to 2 hours, the aluminum piece is fixed on an electrolyzing pool and is used as the anode, the single surface of the anode of the aluminum piece and the solution are in contact, and the conditions of the anode voltage of 10 to 150 V and the temperature of 0 to 25 DEG C are the electrolyzing conditions; (3) a disordered aluminum oxide film generated on the surface of the aluminum piece is washed by acid solution; (4) the electrolyzing process for the second time is carried out, and the conditions of the voltage of 10 to 150 V in the acid solution and the time of 3 to 10 hours according to the thickness of the needed aluminum-oxide film are the electrolyzing conditions; (5) electric chemistry pulse is used, proper film stripping liquid is selected, and high voltage for short time is applied to obtain the ordered through-hole aluminum-oxide film. The present invention can further obtain the needed self-supporting ordered through-hole aluminum-oxide film, and the holes of the film are not corroded.
Description
Technical field
The present invention relates to a kind of preparation method of self-supporting ordered through hole alumina film, belong to the materials chemistry field.
Background technology
At present, preparing self-supporting ordered through hole alumina film method commonly used is: aluminium flake is after series of preprocessing processes such as annealing, degreasing, deoxidation thing and polishing, anode oxidation film-forming by one or many, by two traditional step chemical etching methods removal aluminium substrate and the oxide compound barrier layer at the bottom of the hole, obtain self-supporting ordered through hole alumina film again.The chemical corrosion stripping technology that this method the is used beavy metal impurity ion that will in pellumina, induce one, and cause widening of orderly fenestra; Recently, have report to use the ion sputtering method to carry out stripping, but this method needs expensive specialized equipment, and still need chemical corrosion to remove aluminium substrate.Obviously, the loaded down with trivial details complexity of production technique of above-mentioned pellumina preparation method has a big risk, the cost height, thus limited the suitability for industrialized production of multiaperture pellumina.
Summary of the invention
The present invention seeks to: propose a kind of low cost, simple, controllable aperture, and can prepare the novel method of self-supporting ordered through hole alumina film according to experiment or production technique practical purpose.
Utilize the method for preparing self-supporting ordered through hole alumina film provided by the present invention, step is that the direct degreasing of aluminium flake of (1) surfacing removes the oxide compound pre-treatment; (2) be fixed on the electrolyzer as anode with pretreated aluminium flake, do negative electrode with clean aluminium flake in addition, in concentration is to stir in the acidic solutions such as oxalic acid, sulfuric acid and phosphoric acid of 0.3-0.5M or violent stirring is carried out the electrolysis first time, generally under stirring or violent stirring condition, the time is 0.5-2 hour.Electrolytic condition is: anode voltage is 10-150V, and temperature is a room temperature, generally gets 0-25 ℃, generally with aluminium flake anode single face contact solution; (3) with chromic acid and phosphoric acid mixed solution (6wt%H
3PO
4+ 1.8wt%H
2CrO
4The aqueous solution) the unordered pellumina that generates of flush away surface, in 50-70 ℃ of water-bath ultrasonic immersion more than 30 minutes after, secondary water is ultrasonic to be cleaned; (4) carry out the electrolysis second time, electrolytic condition is with for the first time condition is identical, and the thickness that the time is looked required pellumina is decided to be 3-10 hour, and as electrolysis time 4 hours, characterizing this moment gained pellumina thickness was 15 μ m; (5) use the electrochemistry pulse, select suitable stripper solution, impose high voltage in short-term again, obtain required ordered through hole alumina film.
The pellumina outward appearance that obtains is rounded, and stereoscan photograph shows, diaphragm-operated front (with the solution contact surface) the uniform sequential arrangement in hole, and open at the bottom of the hole fully bottom surface (with the aluminium substrate contact surface).This method can be by changing the aperture of electrolytic experiment condition and reaming condition controlled oxidation aluminium film, and can be by the thickness of electrolysis time controlling diaphragm for the second time, then available secondary of the degree of order of film or electrolytic process or prolong for the first time electrolysis time and control repeatedly.
The preparation method of self-supporting ordered through hole alumina film comprises the steps (seeing accompanying drawing 1): (1) cuts into square (40mm * 40mm), without annealing and polishing process, directly carry out degreasing and go the oxide on surface pre-treatment with kaolin; (2) as accompanying drawing 2 devices pretreated aluminium flake is fixed on the homemade one-sided oxygen constant temperature electrolyzer as anode, and be negative electrode with another large-area clean aluminium flake, select suitable electrolyte solution and electrolytic condition, the constant potential system carries out electrolysis with self-control, and is equipped with self-editing windows software program electrical signal is carried out digitizing output; (3) electrolytic process comprised for three steps: after the certain hour anodic oxidation, form the unordered pellumina of combining closely through degreasing, the pretreated aluminium flake of deoxidation thing on aluminium substrate; Use the above-mentioned unordered pellumina of chromic acid and phosphoric acid solution flush away under certain condition, aluminium substrate can not be corroded in this process; With the first time electrolytic condition identical, the fresh aluminium substrate that obtains is carried out electrolysis second time, select electrolysis time for the second time according to desired thickness, electrolysis is cleaned electrolytic system with redistilled water after finishing; (4) stripper solution is placed electrolyzer, select suitable stripping condition, apply suitable pulse potential being coated with on the aluminium electrode of pellumina, self-supporting ordered through hole alumina film then comes off from substrate voluntarily, with stand-by after the self-supporting ordered through hole alumina film usefulness coordinative solvent cleaning, drying that obtain.
As shown from the above technical solution, the preparation method of self-supporting ordered through hole alumina film of the present invention utilizes two-step anodization, has omitted annealing and polishing pre-treatment step, the pellumina that obtains combining closely on the anode aluminium substrate; Use the electrochemical potential pulsed technique again, select suitable stripper solution and impulsive condition, the process that self-supporting ordered through hole alumina film is broken away from from the substrate voluntarily.Know that from the preparation method this method does not need aluminium flake is annealed and polished finish and relevant equipment thereof, step is simple, the whole process of preparation devoid of risk; Therefore without the chemical corrosion method stripping, can avoid the contaminated and fenestra of film to be widened, better the control punch parameter.This method cost is low, very easily is used more widely.
Description of drawings
Fig. 1 is the process synoptic diagram of preparation self-supporting ordered through hole alumina film of the present invention
Fig. 2 is an electrolytic system synoptic diagram of the present invention
Fig. 3 is aluminium flake current-time curvel in anode oxidation process, the corresponding 50V of difference, 0.3 M H
2C
2O
420V, 0.3 M H
2SO
420V, 0.3 M H
3PO
4Condition; Temperature is 20 ℃
Fig. 4 is scanning electron microscope (SEM) photo of pellumina, wherein dynamic atomic microscope (DFM) photo of (A) top view (B) fish-eye view (C) pellumina and aluminium substrate.
1. the water inlet of electrolyzer constant temperature jacket; 2. the electrolyzer pond body that has constant temperature jacket;
3. electrolyte solution; 4. stirring magneton;
5. the side perforate of clean big area aluminium flake-negative electrode 6. electrolyzers bottom;
7.PDMS packing ring; 8. aluminium flake anode;
9. copper constant temperature jacket; 10. the screw of four jiaos of copper constant temperature jackets;
11. copper constant temperature jacket water-in 12. bronze medal constant temperature jacket water outlets;
13. electrolyzer constant temperature jacket water outlet; 14. connect the lead of constant voltage power supply and two aluminium electrodes;
15. homemade computer-controlled power supply 16. arc synthetic glass fixed jackets;
17. the synthetic glass bottom outlet matches with the electrolyzer inhalent siphon;
18. the synthetic glass threaded hole, the screw that the copper box is four jiaos matches.
Embodiment
Provided process synoptic diagram A that the present invention prepares self-supporting ordered through hole alumina film among Fig. 1 for behind the electrochemical oxidation for the first time, the pellumina that on the anode aluminium substrate, forms; B has removed the anode aluminium substrate behind the pellumina among the A, and the spill that stays is the nucleation centre of the alumilite process second time, plays inducing action, to improve the degree of order of pellumina pore distribution; The ordered aluminum oxide film that C generates after for anodic oxidation for the second time is obstacle aluminum oxide thin layer closely at the bottom of the hole, combine closely with the anode aluminium substrate; D be in certain stripping solution and certain impulsive condition under, the self-supporting ordered through hole alumina film that comes off voluntarily from substrate; E is the anode aluminium substrate after ordered through hole alumina film comes off.
As shown in Figure 2, the method for preparing self-supporting ordered through hole alumina film provided by the invention mainly is:
(1) with smooth aluminium flake after the acetone degreasing, soak to remove its oxide on surface with sodium hydroxide solution; Design the constant temperature electrolyzer of one-sided oxidation and the fixing copper constant temperature sleeve of aluminium flake.Thermostat(t)ed water is drawn from thermostatic bath, by the copper constant temperature sleeve, is derived by electrolyzer constant temperature jacket water outlet and enters Water Tank with Temp.-controlled, forms the constant temperature system water cycle, and this thermostat can guarantee that aluminium flake and electrolyte temperature are constant; This electrolyzer has the constant temperature outer shell, and the side perforate of cell wall polishes around the glass side opening, will be equipped with seal washer between glass and aluminium flake anode.When guaranteeing that above-mentioned aluminium flake anode is fixed on electrolyzer, single face contact solution, the contact surface of aluminium flake anode and solution is circular.Design a square copper box fixedly on aluminium flake and the electrolyzer, the hole of a Φ 5mm is respectively opened on four summits; Respectively there are a water-in and water outlet in the box both sides, link to each other with water-in on the electrolyzer bottle wall shell by Outer Tube, and like this, the position of copper box guarantees that aluminium flake anodic temperature is identical with the temperature of solution in the electrolyzer, and all the temperature with thermostat(t)ed water is consistent.Matching fixedly with the copper box, the aluminium flake anodic is semicircle synthetic glass, be installed in the opposite of glass electrolyzer side circular hole by the side perforate, its section is drilled with four Φ 5mm threaded holes (Fig. 2-18), corresponding with four holes (Fig. 2-10) on the copper coin, again with the screw of four Φ 5mm with copper coin and synthetic glass anchor fixedly aluminum anode on electrolyzer.
(2) used power supply is the 0-80V voltage stabilized source for the range of design voluntarily.
(3) will be installed in the described electrolyzer system of process (2) through the pretreated aluminium flake of process (1) is anode, behind the check system no leakage, adds electrolytic solution, does negative electrode with the big area aluminium flake of cleaning, constitutes two electrolysis systems;
(4) work out the communication interface of homemade constant voltage power supply and Personal Computer dialogue with the Delphi program software, realize that (but constant potential is 0-80V to the computer control electrolytic potential, precision is 0.1%), this system can be a numerary signal with the Faradaic current signal transition of input, with text output, data can be by the Origin routine processes;
(5) power supply in the step (4) is connected in the step (3) is fixed on the two poles of the earth of electrolyzer, magneton in the electrolyte solution (Fig. 2-4) stirs, and carries out the electrolysis first time 0.5-2 hour, obtains unordered pellumina, pours out electrolytic solution, cleans electrolytic system;
(6) use 6%H
3PO
4+ 1.8%H
2CrO
4Mixed water solution, in 60 ℃ of water-baths ultrasonic immersion more than 30 minutes after, clean with secondary water is ultrasonic;
(7) set by step (5) are connected constant voltage power supply with the anode and cathode of electrolyzer, and carry out the electrolysis second time 3-10 hour under the electrolytic condition identical with step (5), obtain ordered through hole alumina film on anode aluminium surface, with the ultrasonic clean electrolytic system of secondary water;
(8) in the electrolyzer of step (7), add HClO
4(70%w/w) with (CH
3CO)
21) or the mixed solution of PEG (98%) (v/v=1:, on the aluminium electrode of capping oxidation aluminium film, apply than the voltage pulse that becomes the high 5V to 10V of membrane voltage and carry out stripping, burst length is 3 to 10 seconds, or uses repeatedly potential pulse to carry out stripping, and the burst length is 3 seconds; After self-supporting ordered through hole alumina film then comes off from aluminium substrate voluntarily, clean with acetone is ultrasonic, clean with secondary water washing again; Select suitable electrolyte solution to carry out stripping.The effect of selection electric field hydrotropy is strong but the relative more weak perchloric acid strong solution of chemical dissolution effect is carried out the electrochemical membrane stripping, and other adds a kind of suitable resisting medium, to disperse the high density proton, prevents the corrosion of pellumina hole wall; Selection with become membrane voltage identical or when comparing into the high 0-5V of membrane voltage, but the part stripping; And when selecting compare into the high 5-10V of membrane voltage, 3 seconds potential pulse in short-term is the solvable aluminum oxide barrier layer that goes at the bottom of the hole, and makes multiaperture pellumina and aluminum anode substrate complete rupture, thereby obtains the ordered porous alumina film of self-supporting, whole through holes.Resisting medium polyoxyethylene glycol, butyleneglycol etc.
(9) to place moisture eliminator to preserve stand-by for the anodic alumina films after will cleaning, or get fragment and characterize its surface topography with scanning electronic microscope, obtains parameters such as pore size, porosity, hole thickness, pitch of holes.As shown in Figure 3, three curve correspondences are at 50V, 0.3 M H
2C
2O
420V, 0.3 M H
2SO
420V, 0.3M H
3PO
4The result who obtains under 20 ℃ of conditions is ordered through hole alumina film.Shown in the photo of Fig. 4.
Claims (7)
1, the preparation method of self-supporting ordered through hole alumina film: the direct degreasing of aluminium flake that it is characterized in that (1) surfacing removes the oxide compound pre-treatment; (2) with pretreated aluminium flake as anode, do negative electrode with clean aluminium flake in addition, in acidic electrolyte solution, carry out the electrolysis first time, time is 0.5-2 hour, aluminium flake is fixed on the electrolyzer as anode, aluminium flake anode single face contact solution, electrolytic condition is: anode voltage 10-150V, temperature is 0-25 ℃; (3) the unordered pellumina that generates with acidic solution flush away surface; (4) carry out the electrolysis second time, electrolytic condition is: in the acidic solution of 10-150V, the thickness that the time is looked required pellumina is decided to be 3-10 hour; (5) use the electrochemistry pulse, select HClO
4(70%w/w) with (CH
3CO)
2(98%) (v/v=1: 1) be stripper solution, on the aluminium electrode of capping oxidation aluminium film, apply than the voltage pulse that becomes the high 5V to 10V of membrane voltage and carry out stripping that the burst length is 3 to 10 seconds, obtains required ordered through hole alumina film.
2, the method for preparing self-supporting ordered through hole alumina film according to claim 1: it is characterized in that carrying out being placed on 6wt%H after the electrolysis first time
3PO
4+ 1.8wt%H
2CrO
4In the mixed water solution, ultrasonic immersion after 30 minutes in 50-70 ℃ of water-bath, ultrasonic cleaning; Electrolysis for the second time is with condition is identical for the first time, and the concentration of solution is 0.3-0.5M.
3, the method for preparing self-supporting ordered through hole alumina film according to claim 1 and 2 is characterized in that electrolytic acidic solution is H
2C
2O
4, H
2SO
4Or H
3PO
4Solution.
4, according to claim 1 or the 2 described methods that prepare self-supporting ordered through hole alumina film, it is characterized in that electrolyzer has the constant temperature outer shell, the perforate of cell wall side guarantees above-mentioned aluminium flake anode single face contact solution; The aluminium flake anode is fixed on electrolyzer, and the face that contacts with the aluminium flake anode is for circular, and the hole of a Ф 5mm is respectively opened on four summits.
5, according to claim 1 or the 2 described methods that prepare self-supporting ordered through hole alumina film, it is characterized in that design has a bronze medal box that the aluminium flake anode is fixed on the electrolyzer, respectively there are a water-in and water outlet in the box both sides, link to each other with water-in on the electrolyzer bottle wall shell by Outer Tube, the position of copper box guarantees that aluminium flake anodic temperature is identical with the temperature of solution in the electrolyzer, and all the temperature with thermostat(t)ed water is consistent; Match fixedly with the copper box that the aluminium flake anodic is semicircle synthetic glass, be installed in the opposite of glass electrolyzer side circular hole by the side perforate.
6, according to the method for preparing self-supporting ordered through hole alumina film described in the claim 4, it is characterized in that the glass side opening of electrolyzer polishes, to be equipped with seal washer between glass and aluminium flake anode.
7,, it is characterized in that used power supply is that range is the voltage stabilized source of 0-80V according to claim 1 or the 2 described methods that prepare self-supporting ordered through hole alumina film.
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| CNB2004100649210A CN1330794C (en) | 2004-10-12 | 2004-10-12 | Preparation for self-supporting ordered through hole alumina film |
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|---|---|---|---|
| CNB2004100649210A CN1330794C (en) | 2004-10-12 | 2004-10-12 | Preparation for self-supporting ordered through hole alumina film |
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| CN1330794C true CN1330794C (en) | 2007-08-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100460327C (en) * | 2006-01-23 | 2009-02-11 | 中国科学院化学研究所 | Process for preparing highly-hydrophilic alumina film material |
| CN1900381B (en) * | 2006-07-04 | 2010-05-12 | 浙江大学 | Device for preparing single surface anode aluminum oxide templete |
| CN101210337B (en) * | 2006-12-29 | 2010-08-25 | 新疆众和股份有限公司 | Method for stripping oxide film of nano aluminum anode |
| CN102953107B (en) * | 2011-08-16 | 2016-03-09 | 国家纳米科学中心 | Prepare the apparatus and method of porous alumina membrane |
| CN102277607B (en) * | 2011-08-17 | 2013-07-10 | 中国科学院金属研究所 | Method for preparing through hole anode alumina film with controllable aperture and thickness |
| RU2489768C1 (en) * | 2012-01-16 | 2013-08-10 | Федеральное государственное бюджетное учреждение науки Институт радиотехники и электроники им. В.А. Котельникова Российской академии наук | Method of producing porous layer of aluminium oxide on insulating substrate |
| RU2495963C1 (en) * | 2012-09-25 | 2013-10-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский университет "МИЭТ" (МИЭТ) | Method of producing porous anodic titanium oxide |
| US9287106B1 (en) | 2014-11-10 | 2016-03-15 | Corning Incorporated | Translucent alumina filaments and tape cast methods for making |
| RU2645237C1 (en) * | 2017-01-09 | 2018-02-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования Северо-Кавказский горно-металлургический институт (государственный технологический университет) (СКГМИ (ГТУ) | Method for producing nanoscale porous anode aluminium oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5696091A (en) * | 1979-12-28 | 1981-08-03 | Showa Alum Corp | Formation of light-colored oxide coating on aluminum surface |
| JPS56166396A (en) * | 1980-05-26 | 1981-12-21 | Furukawa Alum Co Ltd | Formation of bright self-coloring anodically oxidized film of aluminum or its alloy |
| JPH01184912A (en) * | 1988-01-20 | 1989-07-24 | Matsushita Electric Ind Co Ltd | Electrode foil for aluminum electrolytic capacitor and manufacture thereof |
| CN1393587A (en) * | 2001-06-25 | 2003-01-29 | 东海工业缝纫机株式会社 | Embroidery sewing machine and its controlling method |
-
2004
- 2004-10-12 CN CNB2004100649210A patent/CN1330794C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5696091A (en) * | 1979-12-28 | 1981-08-03 | Showa Alum Corp | Formation of light-colored oxide coating on aluminum surface |
| JPS56166396A (en) * | 1980-05-26 | 1981-12-21 | Furukawa Alum Co Ltd | Formation of bright self-coloring anodically oxidized film of aluminum or its alloy |
| JPH01184912A (en) * | 1988-01-20 | 1989-07-24 | Matsushita Electric Ind Co Ltd | Electrode foil for aluminum electrolytic capacitor and manufacture thereof |
| CN1393587A (en) * | 2001-06-25 | 2003-01-29 | 东海工业缝纫机株式会社 | Embroidery sewing machine and its controlling method |
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| CN1614102A (en) | 2005-05-11 |
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