CN103382568A - Preparation method for nanometer porous anodized aluminum membrane - Google Patents
Preparation method for nanometer porous anodized aluminum membrane Download PDFInfo
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- CN103382568A CN103382568A CN 201210135937 CN201210135937A CN103382568A CN 103382568 A CN103382568 A CN 103382568A CN 201210135937 CN201210135937 CN 201210135937 CN 201210135937 A CN201210135937 A CN 201210135937A CN 103382568 A CN103382568 A CN 103382568A
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Abstract
The invention discloses a preparation method for a nanometer porous anodized aluminum membrane. According to the invention, an aluminum sheet having undergone chemical polishing is used for preparing a nanometer anodized porous template with small compact pores, with sulfuric acid used as an electrolyte; constant current electrolytic oxidation is employed for preparing a porous anodized aluminum nanometer template; oxidation efficiency is high, alumina nano-pores in the template are orderly and well aligned, the quality of the template is good, and the product, the nanometer porous anodized aluminum membrane, is regular. A technical problem to overcome is to improve operability in preparation of the nanometer porous alumina template. Through usage of constant current electrolytic oxidation, preparation difficulty is effectively reduced, oxidation efficiency is improved, the growth speed of the template reaches 3 to 5 mu m/h, distribution of nano-pore arrays is uniform and consistent, and the quality of the template is high.
Description
Technical field
The present invention relates to a kind of preparation of nano-form, particularly a kind of preparation method of nano porous anodised aluminum mould.
Background technology
aluminium is more active metal, can form the approximately oxide film of hundreds of nanometer of thick layer in air, this layer oxide film is amorphous, thin and porous, physical strength is low, can't satisfy the requirement of functionalized application, in order to obtain the pellumina of specific function, must process the aluminium surface, aluminium is being carried out electrolysis treatment as anode, at aluminium Surface Creation oxide film, become alumilite process, anodic alumina films is divided into barrier type and multi-hole type two classes, usually can obtain fine and close barrier type oxide film at the neutral electrolyte Anodic Oxidation, and at oxalic acid, phosphoric acid, sulfuric acid etc. self have that in the acid electrolyte of certain oxidation capacity, oxidation can obtain Porosity anodic oxide film, the blocking layer that this Porosity anodic oxide film is fine and close by bottom thin and bed thickness and loose porous layer consists of on it, the film born of the same parents of porous layer are that hexagonal Mi Dui arranges, the hole of a nano-scale of each film born of the same parents center existence, and hole size is even, with the aluminum substrate Surface Vertical.
Due to unique texture and the advantage of porous anodic alumina films, for research and the preparation of novel material provides a kind of new approaches and methods.At present, porous anodic alumina films not only absorbs the aspects such as lane, support of the catalyst and preparations of nanomaterials in separatory membrane, optics and electronic component, magneticthin film, selectivity and all is widely used, particularly having great importance aspect the uniform nano structural material of preparation size, is the desirable template of even material preparation, such as being used for synthesis of nano line, nanotube etc.
Take sulfuric acid, oxalic acid or phosphoric acid as electrolytic solution, near the anodic oxidation custom of carrying out the optimum value of oxidation voltage is called gentle anonizing mild anodization, be called MA, its shortcoming is that the speed of growth for preparing multiaperture pellumina only has 2 μ m/h, production rate is slow, and production efficiency is low.
Summary of the invention
For addressing the above problem, the invention discloses a kind of preparation method of nano porous anodised aluminum film, adopt the mode of continuous current oxidation preparation, effectively reduced the preparation difficulty, improved oxidation efficiency, the speed of growth of template reaches 80-120 μ m/h, and nanohole array is evenly distributed unanimously, and template quality is high.
The preparation method of nano porous anodised aluminum film disclosed by the invention comprises the steps:
A, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, and polishing time is 20-40s, and solution is the NaOH solution of 1.00mol/L, then aluminium flake is immersed the deionized water for ultrasonic ripple and cleans 10s;
B, the aluminium flake after the steps A polished finish is placed in the continuous current oxidation pond, strength of current is 10-40mA, and electrolysis time is 1h-3h, and electrolytic solution is the sulphuric acid soln of 0.5-1.5mol/L, and electrolytic environments is ice-water bath, induction stirring;
C, the anodic alumina film that step B is obtained immerse deionized water for ultrasonic ripple washing 20-40s, naturally dry afterwards.
The preparation method of nano porous anodised aluminum film disclosed by the invention, by adopting take sulfuric acid as electrolytic solution, the polishing aluminium flake is electrode, the continuous current oxidation prepares Electrochemical anodization, production technique is simple, and is easy to operate, and oxidation efficiency is high, on template, the nanoporous size uniform is consistent, arrange in order, the Electrochemical anodization good product quality, production efficiency is high, preferably control the production cost of pellumina, reduced production cost.
A kind of improvement of the preparation method of nano porous anodised aluminum film disclosed by the invention, in step B, the anode and cathode of continuous current oxidation pond all adopts resulting polishing aluminium flake in steps A.This improvement is by adopting the polishing aluminium flake as the anode and cathode of continuous current oxidation, be conducive to promote normally carrying out of electrolysis, the aluminium flake of avoiding being untreated is cooked electrode pair electrolytic solution and is polluted, affect and anodisedly normally carry out, thereby cause the excessive electrode surface that makes of local current to be burnt, affect normally carrying out of oxidation.
Another of the preparation method of nano porous anodised aluminum film disclosed by the invention improved, and in steps A, the purity of aluminium flake is 99.99%.This improvement adopts the high purity aluminium flake as the electrolytic oxidation material, has effectively avoided the appearance of the bad oxidation template of string fire damage situation in the electrolytic acid cleaning oxydation process, is conducive to the normal manufacture of product, has improved yield rate and production efficiency, has reduced production cost.
Another of the preparation method of nano porous anodised aluminum film disclosed by the invention improved, and in step B, the stir speed (S.S.) of induction stirring is 40-80round/min.This improvement has guaranteed the well-beaten while of electrolytic solution has been avoided again too kicking up of electrolytic solution by limiting stirring velocity, thereby affect the fluctuation of electrolysis electrode area, and electrolysis voltage is exerted an influence, thereby may cause electrode burn, affect normally carrying out of electrolysis work.
the preparation method of nano porous anodised aluminum film disclosed by the invention, by adopting take sulfuric acid as electrolytic solution, electrode is the polishing aluminium flake, the continuous current oxidation prepares Electrochemical anodization, production technique is simple, easy to operate, oxidation efficiency is high, on template, the nanoporous size uniform is consistent, arrange in order, the Electrochemical anodization good product quality, production efficiency is high, preferably controlled the production cost of pellumina, reduced production cost, effectively avoided the electrode burn that the reasons such as electrode array fire cause and interrupted the appearance of the situations such as oxidation, simultaneously by limiting stirring velocity, guaranteed the well-beaten while of electrolytic solution, avoided again too kicking up of electrolytic solution, thereby affect the fluctuation of electrolysis electrode area, and electrolysis voltage is exerted an influence, thereby may cause electrode burn, affect normally carrying out of electrolysis work.
Description of drawings
The SEM photo of the porous anodic alumina films of preparation method's preparation of Fig. 1, nano porous anodised aluminum film disclosed by the invention;
The preparation method's of Fig. 2, nano porous anodised aluminum film disclosed by the invention U-t image.
Embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate the present invention, should understand following embodiment and only be used for explanation the present invention and be not used in and limit the scope of the invention.
As depicted in figs. 1 and 2, the preparation method of nano porous anodised aluminum film disclosed by the invention comprises the steps:
A, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, and polishing time is 20-40s, and solution is the NaOH solution of 1.00mol/L, then aluminium flake is immersed the deionized water for ultrasonic ripple and cleans 10s;
B, the aluminium flake after the steps A polished finish is placed in the continuous current oxidation pond, strength of current is 10-40mA, and electrolysis time is 1h-3h, and electrolytic solution is the sulphuric acid soln of 0.5-1.5mol/L, and electrolytic environments is ice-water bath, induction stirring;
C, the anodic alumina film that step B is obtained immerse deionized water for ultrasonic ripple washing 20-40s, naturally dry afterwards.
The preparation method of nano porous anodised aluminum film disclosed by the invention, by adopting take sulfuric acid as electrolytic solution, the polishing aluminium flake is electrode, the continuous current oxidation prepares Electrochemical anodization, production technique is simple, and is easy to operate, and oxidation efficiency is high, on template, the nanoporous size uniform is consistent, arrange in order, the Electrochemical anodization good product quality, production efficiency is high, preferably control the production cost of pellumina, reduced production cost.
As a kind of preferred, in step B, the anode and cathode of continuous current oxidation pond all adopts resulting polishing aluminium flake in steps A.By adopting the polishing aluminium flake as the anode and cathode of continuous current oxidation, be conducive to promote normally carrying out of electrolysis, the aluminium flake of avoiding being untreated is cooked electrode pair electrolytic solution and is polluted, affect and anodisedly normally carry out, thereby cause the excessive electrode surface that makes of local current to be burnt, affect normally carrying out of oxidation.
As a kind of preferred, in steps A, the purity of aluminium flake is 99.99%.Adopt the high purity aluminium flake as the electrolytic oxidation material, effectively avoided the appearance of the bad oxidation template of string fire damage situation in the electrolytic acid cleaning oxydation process, be conducive to the normal manufacture of product, improved yield rate and production efficiency, reduced production cost.
As a kind of preferred, in step B, the stir speed (S.S.) of induction stirring is 40-80round/min.By limiting stirring velocity, guaranteed the well-beaten while of electrolytic solution has been avoided again too kicking up of electrolytic solution, thereby affect the fluctuation of electrolysis electrode area, and electrolysis voltage is exerted an influence, thereby may cause electrode burn, affect normally carrying out of electrolysis work.
As shown in Figure 1, the hole born of the same parents of the alumina formwork of the present invention's preparation are cylindricality, the nanoporous close-packed arrays, and the aperture is 20-40nm.As shown in Figure 2, at the electrolysis initial stage, electrolytic oxidation voltage sharply rises to approximately 49V-50V of maximum, then descend and form a spike, then oxidation voltage is stable, and this is due at the oxidation initial stage, and pellumina forms gradually simultaneously that thickness increases, so electrolysis voltage is just along with rising, when beginning to form array hole on anode, voltage drop is after anodic oxidation reactions is normal, the barrier layer thickness of anodised aluminium bottom is stable, and electrolysis voltage just was attributed to and stablely finished to oxidizing reaction this moment.
Embodiment 1, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, polishing time is 20s, and polishing fluid is the NaOH solution of 1.00mol/L, then aluminium flake is carried out ultrasonic cleaning 10s again through immersing in deionized water after deionized water rinsing; Aluminium flake after polished finish is placed in the continuous current oxidation pond, switches on power, strength of current is 10mA, and electrolysis time is 1h, and electrolytic solution is the sulphuric acid soln of 0.5mol/L, and electrolytic environments is ice-water bath, induction stirring, stir speed (S.S.) 40round/min; The anodic alumina film that step B is obtained immerses deionized water for ultrasonic ripple washing 20s, naturally dries afterwards.Sample Scan tunneling electron microscopy, template thickness 3.2 μ m, aperture 20nm.
Embodiment 2, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, polishing time is 25s, and polishing fluid is the NaOH solution of 1.00mol/L, then aluminium flake is carried out ultrasonic cleaning 10s again through immersing in deionized water after deionized water rinsing; Aluminium flake after polished finish is placed in the continuous current oxidation pond, switches on power, strength of current is 20mA, and electrolysis time is 2h, and electrolytic solution is the sulphuric acid soln of 1.0mol/L, and electrolytic environments is ice-water bath, induction stirring, stir speed (S.S.) 60round/min; The anodic alumina film that step B is obtained immerses deionized water for ultrasonic ripple washing 20s, naturally dries afterwards.Sample Scan tunneling electron microscopy, template thickness 6.7 μ m, aperture 33nm.
Embodiment 3, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, polishing time is 30s, and polishing fluid is the NaOH solution of 1.00mol/L, then aluminium flake is carried out ultrasonic cleaning 10s again through immersing in deionized water after deionized water rinsing; Aluminium flake after polished finish is placed in the continuous current oxidation pond, switches on power, strength of current is 30mA, and electrolysis time is 2.5h, and electrolytic solution is the sulphuric acid soln of 1.5mol/L, and electrolytic environments is ice-water bath, induction stirring, stir speed (S.S.) 80round/min; The anodic alumina film that step B is obtained immerses deionized water for ultrasonic ripple washing 20s, naturally dries afterwards.Sample Scan tunneling electron microscopy, template thickness 8.4 μ m, aperture 40nm.
Embodiment 4, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, polishing time is 40s, and polishing fluid is the NaOH solution of 1.00mol/L, then aluminium flake is carried out ultrasonic cleaning 10s again through immersing in deionized water after deionized water rinsing; Aluminium flake after polished finish is placed in the continuous current oxidation pond, switches on power, strength of current is 40mA, and electrolysis time is 3h, and electrolytic solution is the sulphuric acid soln of 1.0mol/L, and electrolytic environments is ice-water bath, induction stirring, stir speed (S.S.) 50round/min; The anodic alumina film that step B is obtained immerses deionized water for ultrasonic ripple washing 20s, naturally dries afterwards.Sample Scan tunneling electron microscopy, template thickness 14 μ m, aperture 42nm.
the preparation method of nano porous anodised aluminum film disclosed by the invention, by adopting take sulfuric acid as electrolytic solution, electrode is the polishing aluminium flake, the continuous current oxidation prepares Electrochemical anodization, production technique is simple, easy to operate, oxidation efficiency is high, on template, the nanoporous size uniform is consistent, arrange in order, the Electrochemical anodization good product quality, production efficiency is high, preferably controlled the production cost of pellumina, reduced production cost, effectively avoided the electrode burn that the reasons such as electrode array fire cause and interrupted the appearance of the situations such as oxidation, simultaneously by limiting stirring velocity, guaranteed the well-beaten while of electrolytic solution, avoided again too kicking up of electrolytic solution, thereby affect the fluctuation of electrolysis electrode area, and electrolysis voltage is exerted an influence, thereby may cause electrode burn, affect normally carrying out of electrolysis work.
The disclosed technique means of the present invention program is not limited only to the disclosed technique means of above-mentioned technique means, also comprises the technical scheme that is comprised of above technical characterictic arbitrary combination.
Claims (4)
1. the preparation method of a nano porous anodised aluminum film, it is characterized in that: the preparation method of described nano porous anodised aluminum film comprises the steps:
A, annealed aluminium flake is carried out the continuous current electrochemical etching, size of current is 10mA, and polishing time is 20-40s, and solution is the NaOH solution of 1.00mol/L, then aluminium flake is immersed the deionized water for ultrasonic ripple and cleans 10s;
B, the aluminium flake after the steps A polished finish is placed in the continuous current oxidation pond, strength of current is 10-40mA, and electrolysis time is 1h-3h, and electrolytic solution is the sulphuric acid soln of 0.5-1.5mol/L, and electrolytic environments is ice-water bath, induction stirring;
C, the anodic alumina film that step B is obtained immerse deionized water for ultrasonic ripple washing 20-40s, naturally dry afterwards.
2. the preparation method of nano porous anodised aluminum film according to claim 1, it is characterized in that: in described step B, the anode and cathode of continuous current oxidation pond all adopts resulting polishing aluminium flake in steps A.
3. the preparation method of nano porous anodised aluminum film according to claim 1, it is characterized in that: in described steps A, the purity of aluminium flake is 99.99%.
4. the preparation method of nano porous anodised aluminum film according to claim 1, it is characterized in that: in described step B, the stir speed (S.S.) of induction stirring is 40-80round/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734541A (en) * | 2016-04-05 | 2016-07-06 | 新乡学院 | Method for preparing high-temperature superconducting film transition layer on aluminum oxide crystalline substrate |
| CN105803434A (en) * | 2016-04-05 | 2016-07-27 | 新乡学院 | Method for preparing high-temperature superconducting thin film on aluminum oxide crystal substrate |
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- 2012-05-04 CN CN 201210135937 patent/CN103382568A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734541A (en) * | 2016-04-05 | 2016-07-06 | 新乡学院 | Method for preparing high-temperature superconducting film transition layer on aluminum oxide crystalline substrate |
| CN105803434A (en) * | 2016-04-05 | 2016-07-27 | 新乡学院 | Method for preparing high-temperature superconducting thin film on aluminum oxide crystal substrate |
| CN105734541B (en) * | 2016-04-05 | 2017-11-07 | 新乡学院 | A kind of method that high-temperature superconducting thin film transition zone is prepared in alpha-alumina crystals substrate |
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Application publication date: 20131106 |