CN103966642B - The preparation method of highly ordered porous anodic film - Google Patents
The preparation method of highly ordered porous anodic 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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- 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
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- 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
Abstract
The invention discloses the preparation method of a kind of highly ordered porous anodic film, including pretreatment and anodic oxidation.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.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.Cobalt salt is Co (NO3)2·6H2O、CoCO3、(NH4)2Co(SO4)2·6H2O、CoSO4·7H2O and CoC2O4In one.The preparation method of the present invention 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, it is very suitable for industrialized great production, and the even aperture distribution of the porous anodic oxide film obtained, there is the order of height.
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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| CN201610597073.2A CN106048688B (en) | 2014-05-22 | 2014-05-22 | A kind of preparation method of highly ordered porous anodic film |
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| 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 |
| US7078154B2 (en) * | 2001-07-06 | 2006-07-18 | Fuji Photo Film Co., Ltd. | Presensitized plate |
| CN1325698C (en) * | 2003-10-21 | 2007-07-11 | 东莞理工学院 | Process for producing ordered porous anodic alumina form |
| 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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| CN106048688A (en) | 2016-10-26 |
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