CN103966642B - Preparation method of highly ordered porous anodic oxide film - Google Patents
Preparation method of highly ordered porous anodic oxide film Download PDFInfo
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- CN103966642B CN103966642B CN201410220482.1A CN201410220482A CN103966642B CN 103966642 B CN103966642 B CN 103966642B CN 201410220482 A CN201410220482 A CN 201410220482A CN 103966642 B CN103966642 B CN 103966642B
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- porous anodic
- ordered porous
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010407 anodic oxide Substances 0.000 title abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229910019167 CoC2 Inorganic materials 0.000 claims abstract description 4
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 claims abstract description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000005498 polishing Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
- Weting (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a preparation method of a highly ordered porous anodic oxide film, which comprises pretreatment and anodic oxidation. And in the step of anodic oxidation, the pretreated pure aluminum is put into electrolyte, and is subjected to anodic oxidation for 1-4 hours at the temperature of-20 ℃ and under the voltage of 80-120V. The electrolyte is an aqueous solution containing phosphoric acid and cobalt salt, and each liter of electrolyte contains 0.1-0.6 mol of phosphoric acid and 0.1-0.8 g of cobalt salt. The cobalt salt being Co (NO)3)2·6H2O、CoCO3、(NH4)2Co(SO4)2·6H2O、CoSO4·7H2O and CoC2O4One kind of (1). According to the inventionThe preparation method only needs one-time anodic oxidation without electrochemical polishing and treatment after polishing, so that the process flow is greatly shortened, the production efficiency is improved, the method is very suitable for industrial mass production, and the obtained porous anodic oxide film has uniform pore size distribution and high orderliness.
Description
Technical field
The invention belongs to field of metal surface treatment technology, be specifically related to the preparation method of a kind of highly ordered porous anodic film.
Background technology
Porous anodic alumina films (AAO) is the aluminum oxide film in surface of pure aluminum formation by the method for electrochemical oxidation with the most regular pore structure.Its membrane structure is hexagon closelypacked cylindricality after birth, the center of each after birth have one nanometer level microporous.
Porous anodic alumina films is heat and the good insulator of electricity, has the features such as hardness is high, wearability is good；Having good corrosion resistance, its resistance to corrosion is decided by the alloying component of thicknesses of layers, composition, porosity and matrix material；The strongest with the adhesion of parent metal, even if film layer is with matrix bending extremely fracture, film layer still can remain good combination with parent metal.
Along with people are to porous anodic alumina films unique microstructures and the understanding of property, porous anodic alumina films is gradually widely used in the various functions fields such as catalysis, magnetic pipe recording material, optics and photoelectric cell, antibacterial film, separation membrane material, sensor, becomes the focus of scholars's research.
At present, the preparation of porous anodic alumina films mainly uses two step anodizings (such as Chinese patent literature CN1609283A, CN101007645A, CN101139730A etc.), the most first aluminium is carried out pretreatment, then aoxidize first in acidic electrolysis bath, oxidization time is usually 1h～5h, then pass through chemical attack and remove the oxide-film aoxidizing generation first, finally in acidic electrolysis bath, carry out secondary oxidation again, oxidization time is usually 2h～12h, obtains porous anodic alumina films.Wherein pretreatment mainly includes cleaning and electrochemical polish, and the Main Function of electrochemical polish is to obtain smoother surface, thus beneficially obtains size and the porous array film more uniformly spread after anodic oxidation.The solution that electrochemical polish uses all is made up of according to certain volume ratio dehydrated alcohol and perchloric acid.The shortcoming of the method is: (1) anodizing time is longer, thus causes the production cycle；(2) the oxide-film degree of order aoxidizing generation first is poor, thus affects the degree of order of the porous anodic alumina films finally given.
Chinese patent literature CN103225096A discloses the preparation method of a kind of porous anodic alumina films, the nanometer porous film layer, anodic oxidation and the cleaning that are formed including pretreatment, electrochemical polish, removal electrochemical polish and drying.The electrolyte that its Anodic Oxidation uses is 0.2mol/L～0.6mol/L phosphate aqueous solution.The deficiency of the document is: (1) is although the most only carrying out an anodic oxidation, but needs before the oxidation to carry out electrochemical polish and treatment fluid membrane removal, and therefore technological process is the longest, is not suitable for industrialized great production.(2) use chromium-containing solution to carry out membrane removal, environment and human body are had bigger harm.(3) carrying out anodic oxidation effect in phosphate aqueous solution the best, the porous anodic alumina films pore-size distribution finally given is wider, and the degree of order is poor.
Summary of the invention
It is an object of the invention to solve the problems referred to above, it is provided that a kind of anodic oxidation effect is preferably and technological process is shorter, be suitable for the preparation method of the highly ordered porous anodic film of industrialized great production.
The technical scheme realizing the object of the invention is: the preparation method of a kind of highly ordered porous anodic film, including pretreatment and anodic oxidation；Described anodic oxidation is to put in electrolyte by pretreated fine aluminium, at a temperature of-20～20 DEG C, 80～the voltage anodic oxygenization 1～4h of 120V；Described electrolyte is the aqueous solution containing phosphoric acid Yu cobalt salt, contains phosphoric acid and the cobalt salt of 0.1～0.8g of 0.1～0.6mol in every liter of electrolyte.
Described cobalt salt is Co (NO3)2·6H2O、CoCO3、(NH4)2Co(SO4)2·6H2O、CoSO4·7H2O and CoC2O4In one.
Described pretreatment is first by fine aluminium soaked in absolute ethyl alcohol 1～5min, is subsequently placed in the natural oxide layer removing surface in the sodium hydroxide solution of 30～80 DEG C, is immediately placed in salpeter solution and carries out acid-base neutralization reaction 5～30s after then taking out.
The concentration of described sodium hydroxide solution is 1～3mol/L.
The concentration of described salpeter solution is 1～3mol/L.
The present invention has positive effect: the method for (1) present invention adds a small amount of cobalt salt composition electrolyte in phosphate aqueous solution, use this electrolyte only need to carry out an anodic oxidation and without the process after electrochemical polish and polishing, this substantially reduces technological process, improve production efficiency, be very suitable for industrialized great production.(2) even aperture distribution of the porous anodic oxide film that the method for the present invention obtains, has the order of height, and anodic oxidation effect is substantially better than prior art.(3) method of the present invention can also prepare the anode oxide film of respective aperture according to specific needs, has the adjustable advantage of pore size.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph on the highly ordered porous anodic film surface that embodiment 1 prepares.
Fig. 2 is the graph of pore diameter distribution of the highly ordered porous anodic film that embodiment 1 prepares.
Detailed description of the invention
(embodiment 1)
The preparation method of the highly ordered porous anodic film of the present embodiment is as follows:
1. pretreatment: first fine aluminium is soaked in dehydrated alcohol 3min, to remove the Organic substance of surface of pure aluminum, then take out and clean with clear water, it is placed in the sodium hydroxide solution that 50 DEG C of concentration is 2mol/L processing 20s, to remove the natural oxide layer of surface of pure aluminum, then it is immediately placed in the salpeter solution that concentration is 2mol/L after taking out and carries out acid-base neutralization reaction 20s, clean with clear water, dry after finally taking out.
2. electrolyte is prepared: by the CoSO of 0.6g4·7H2O joins in the phosphoric acid solution that 300mL concentration is 1mol/L and dissolves, and adds water and supply 1L, obtains electrolyte.
3. anodic oxidation: carrying out anodic oxidation in the electrolyte that 2. step is prepared by putting into through the most pretreated fine aluminium of step, oxidation voltage is 90V, and oxidization time is 1.5h, is controlled oxidizing temperature at 10 DEG C by recirculated cooling water in anode oxidation process.
4. after anodized, use ultrasonic washing with clean water 5min, hot-air seasoning, obtain highly ordered porous anodic film.
The scanning electron microscope (SEM) photograph of the highly ordered porous anodic film that the present embodiment prepares is shown in that Fig. 1, graph of pore diameter distribution are shown in Fig. 2.
By Fig. 1 and Fig. 2 it can be seen that the present embodiment prepare porous anodic oxide film even aperture distribution, have height order.
(embodiment 2～embodiment 5)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is to be shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Cobalt salt | CoSO4·7H2O | Co(NO3)2·6H2O | (NH4)2Co(SO4)2·6H2O | CoCO3 | CoC2O4 |
| Cobalt salt concentration | 0.6g/L | 0.7g/L | 0.4g/L | 0.1g/L | 0.8g/L |
| Phosphoric acid concentration | 0.3mol/L | 0.4mol/L | 0.2mol/L | 0.1mol/L | 0.6mol/L |
| Oxidation voltage | 90V | 110V | 100V | 120V | 120V |
| Oxidization time | 1.5h | 2h | 2.5h | 1h | 4h |
| Oxidizing temperature | 10℃ | 5℃ | 0℃ | 20℃ | -20℃ |
Claims (5)
1. a preparation method for highly ordered porous anodic film, including pretreatment and anodic oxidation；Described anodic oxidation is to put in electrolyte by pretreated fine aluminium, at a temperature of-20～20 DEG C, 80～the voltage anodic oxygenization 1～4h of 120V；It is characterized in that: described electrolyte is the aqueous solution containing phosphoric acid Yu cobalt salt, every liter of electrolyte contains phosphoric acid and the cobalt salt of 0.1～0.8g of 0.1～0.6mol.
The preparation method of highly ordered porous anodic film the most according to claim 1, it is characterised in that: described cobalt salt is Co (NO3)2·6H2O、CoCO3、(NH4)2Co(SO4)2·6H2O、CoSO4·7H2O and CoC2O4In one.
The preparation method of highly ordered porous anodic film the most according to claim 1 and 2, it is characterized in that: described pretreatment is first by fine aluminium soaked in absolute ethyl alcohol 1～5min, it is subsequently placed in the natural oxide layer removing surface in the sodium hydroxide solution of 30～80 DEG C, is immediately placed in salpeter solution after then taking out and carries out acid-base neutralization reaction 5～30s.
The preparation method of highly ordered porous anodic film the most according to claim 3, it is characterised in that the concentration of described sodium hydroxide solution is 1～3mol/L.
The preparation method of highly ordered porous anodic film the most according to claim 3, it is characterised in that: the concentration of described salpeter solution is 1～3mol/L.
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| CN201410220482.1A CN103966642B (en) | 2014-05-22 | 2014-05-22 | Preparation method of highly ordered porous anodic oxide film |
| CN201610597073.2A CN106048688B (en) | 2014-05-22 | 2014-05-22 | Preparation method of highly ordered porous anodic oxide film |
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| CN201410220482.1A CN103966642B (en) | 2014-05-22 | 2014-05-22 | Preparation method of highly ordered porous anodic oxide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3717555A (en) * | 1970-11-27 | 1973-02-20 | Fentron Ind Inc | Method of producing an electrolytic coating on aluminum and the product thereof |
| JPS5613497A (en) * | 1979-07-09 | 1981-02-09 | Toshiba Corp | Electrolytic coloring method for aluminum group metal |
| SU1145061A1 (en) * | 1982-12-06 | 1985-03-15 | Белорусский Ордена Трудового Красного Знамени Государственный Университет Им.В.И.Ленина | Electrolyte for electrochemical painting of anodized aluminium black and method of preparing same |
| KR100439766B1 (en) * | 2001-02-28 | 2004-07-12 | 주식회사 범일 | Color titanium-zirconium alloy and method for manufacturing the same |
| DE60211426T2 (en) * | 2001-07-06 | 2007-05-16 | Fuji Photo Film Co., Ltd., Minami-Ashigara | Presensitized plate for making a lithographic printing plate |
| CN1325698C (en) * | 2003-10-21 | 2007-07-11 | 东莞理工学院 | Preparation method of ordered porous anodic alumina template |
| 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 |
| CN103789808B (en) * | 2012-10-31 | 2017-12-01 | 深圳富泰宏精密工业有限公司 | The surface treatment method and aluminum products of aluminium alloy |
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| CN103966642A (en) | 2014-08-06 |
| CN106048688B (en) | 2017-11-21 |
| CN106048688A (en) | 2016-10-26 |
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