CN1974873A - Fast stable growth process of alumina film with nanometer pore array in relatively great pore distance - Google Patents
Fast stable growth process of alumina film with nanometer pore array in relatively great pore distance Download PDFInfo
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- CN1974873A CN1974873A CN 200610118666 CN200610118666A CN1974873A CN 1974873 A CN1974873 A CN 1974873A CN 200610118666 CN200610118666 CN 200610118666 CN 200610118666 A CN200610118666 A CN 200610118666A CN 1974873 A CN1974873 A CN 1974873A
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Abstract
The fast stable growth process of alumina film with nanometer pore array in relatively great pore distance includes the following steps: 1. compounding electrolyte solution with H3PO4, C2H5OH and water; 2. pre-treating aluminum sheet through soaking in acetone, wipping, rinsing with deionized water and electrochemical polishing with mixed solution of perchloric acid and ethanol; 3. the first etching of the aluminum sheet in the electrolyte solution at -5 to -10 deg.c under the action of anode oxidizing voltage of 195V and current density of 1500-4000A/sq m; 4. soaking the aluminum sheet in water solution of chromic acid at 60 deg.c to eliminate alumina generated in the first etching; and 5. the second etching of the aluminum sheet in the same condition as that in the step 3.
Description
Technical field
The present invention is a kind of preparation method of technical field of nano material, and specifically, what relate to is a kind of fast stable growth process of alumina film with nanometer pore array of relatively great pore distance.
Background technology
Adopt anodic corrosion technology institute's borolon film owing to protect at anti-corrosion of metal, metal coloring, there is important use aspects such as metal strength design, and the structure design of relevant film, its synthetic technical study have caused that people more and more pay close attention to and interest.From nineteen fifty-three U.S.'s aluminum be equipped with company aluminium research laboratory work up to the mid-90, being engaged in this respect work sutdy personnel institute research system mainly is dense form pellumina and unordered multi-hole type pellumina.Nineteen ninety-five, the H.Masuda of department of chemistry of Kyoto Univ Japan etc. on the Science magazine reported first synthesize Al
2O
3Ordered nano hole array film.Aluminum oxide ordered nano hole array film is because the making method of its unique ordered structure and cheap and simple, make it uniqueness and application prospects be arranged (for example in a lot of fields, magneticstorage, solar cell, photonic crystal etc.), thus cause scientists very big interest and show great attention to.
Utilize oxalic acid and sulfuric acid electrolyte to obtain the aluminum oxide ordered nano hole array film of pitch of holes only, limited of the application of aluminum oxide ordered nano hole array film in some fields less than 100nm.Thereby the alumina film with nanometer pore array of exploitation relatively great pore distance (more than the hundreds of nm) is subjected to showing great attention to of people.Some experimental results show, utilize phosphoric acid electrolyte can realize preparing the orderly hole of the aluminum oxide array film of relatively great pore distance (hundreds of nm), but owing in phosphoric acid electrolyte, carry out anodic oxidation, the response voltage very high (195V) that requires, aluminium flake oxidized reaction in electrolytic solution is very violent, thermal value is very big and very fast, causes experiment not stablize and continues to carry out, and can not obtain the high quality aluminum oxide film with nanometer pore array.So, all require in the experiment to use rapid heat dissipation technology, reaction soln temperature requirement lower (0 ℃) in order to guarantee solution constant temperature, the very fast heat radiation in aluminium flake surface.But under traditional method,, all remain on a low-down growth velocity (less than 200nm min in order to realize the stable growth of alumina film with nanometer pore array
-1) under the condition, and for the required growth time of the alumina film with nanometer pore array that obtains high-quality relatively great pore distance (hundreds of nm) very long (greater than more than 10 hours).
Find through literature search prior art, Sachiko Ono etc. are at Electrochemical andSolid-State Letters (electrochemistry and solid-state wall bulletin, 2004, the 7th phase, the B21-B24 page or leaf) " the Self-Ordering of Anodic Porous Alumina Induced by Local CurrentConcentration:Burning " that delivers on (local current compiles the orderly certainly of inductive anode porous alumina: ablate), high current density is proposed in this article, that is high electric field is to influence the hole to arrange the most important factor of order, adopt the anodic oxidation voltage of 195V, in the phosphoric acid solution of 0.2mol/L, carry out electrolysis, taking place to have observed comparatively orderly hole arrangement around the zone of ablating.Its deficiency is: because ablation phenomen, film can not stable growth, has influenced the total quality of multiaperture pellumina.
Summary of the invention
At the deficiencies in the prior art and defective, the invention provides a kind of fast stable growth process of alumina film with nanometer pore array of relatively great pore distance.The present invention makes electrolyte temperature reduce to subzero ten degree and icing by adding ethanol to reduce its zero pour in electrolytic solution.The ethanol that is added not only can reduce the electrolytic solution zero pour, and can be used as coolant and take away a large amount of heats that produce in the pellumina process of growth.Under this cryogenic environment,, realize (1500-4000A m under the High-Field by conventional whipping appts
-2) quick, the stable growth of anodic alumina films.
The present invention is achieved by the following technical solutions, and concrete steps are:
The first, preparation phosphoric acid-water-ethanol electrolytic solution: H wherein
2O and C
2H
5The OH volume ratio is 4: 1, H
3PO
4Concentration is 0.25-0.5mol/L, and the electrolytic solution cumulative volume is 2L;
Second, the aluminium flake pre-treatment: with diameter is that the circular aluminium flake (purity is more than or equal to 99.999%) of 2cm is put into acetone and soaked 20 minutes, with cotton balls with its surperficial wiped clean, and use deionized water rinsing, using volume ratio is 1: 4 perchloric acid and alcohol mixed solution electrochemical etching under constant-pressure conditions;
The 3rd, use low temperature thermostat bath electrolyte temperature to be reduced to-5～-10 ℃ of temperature, and electrolytic solution is stirred, be that 195V, current density are 1500-4000Am at anodic oxidation voltage
-2Condition under aluminium flake is once corroded some minutes;
The 4th, be to soak some hrs in 60 ℃ phosphoric acid (6wt.%) and chromic acid (1.8wt.%) mixed aqueous solution with the sample after the corrosion once in temperature, to remove the once aluminum oxide of corrosion generation;
The 5th, under the condition identical, sample is carried out anticaustic with the 3rd step, etching time is within ten minutes.
Adopt the porous anodic aluminium oxide of the present invention's preparation, have stable (the 4-10 μ m min of growth fast
-1), all even hole, aperture ordered arrangement degree advantages of higher.Compare with traditional method, the efficient that the present invention will prepare porous anodic alumina films has improved nearly 100 times, and ablation phenomen can not take place in the preparation process, and the film growth is very stable, and aperture homogeneity and hole are arranged the degree of order and also be greatly enhanced.The more important thing is, under the anodic oxidation voltage that keeps 195V, can obtain different oxidation current density (1500-4000A m with conditions such as the area of negative electrode compare by adjusting phosphoric acid concentration, electrolyte temperature, anode
-2), and then obtain the porous anodic alumina films of different pitchs of holes (320-380nm).This porous anodic alumina films that can regulate and control arbitrarily for the acquisition pitch of holes provides a kind of effective means.
Embodiment
Below embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Electrolytic solution is by H
2O, C
2H
5OH and H
3PO
4Formulated, H wherein
2O and C
2H
5The OH volume ratio is 4: 1, H
3PO
4Content is 0.25mol/L, and the electrolytic solution cumulative volume is 2L.With diameter is that the circular aluminium flake (purity is more than or equal to 99.999%) of 2cm is put into acetone and soaked 20 minutes, with cotton balls with its surperficial wiped clean, and use deionized water rinsing, using volume ratio is 1: 4 perchloric acid and alcohol mixed solution electrochemical etching under constant-pressure conditions.Using low temperature thermostat bath electrolyte temperature to be reduced to-5 ℃, is that 195V, current density be 1500mA/m with aluminium flake at anode voltage by the mixer means of routine
2Condition corroded 5 minutes next time.Is to soak 4 hours in 60 ℃ phosphoric acid (6wt.%) and chromic acid (1.8wt.%) mixed aqueous solution the sample after the corrosion once in temperature, to remove the once aluminum oxide of corrosion generation.With once corrode identical condition under, sample was carried out anticaustic 10 minutes.The multiaperture pellumina of preparing is the hexagonal solid matter each other and distributes between the surface tissue unit, the hole distribution height is orderly, and the aperture is 80nm, and pitch of holes is 380nm, and barrier layer thickness is 150nm, and film thickness is about 40 μ m.
Embodiment 2
Electrolytic solution is by H
2O, C
2H
5OH and H
3PO
4Formulated, H wherein
2O and C
2H
5The OH volume ratio is 4: 1, H
3PO
4Content is 0.3mol/L, and the electrolytic solution cumulative volume is 2L.With diameter is that the circular aluminium flake (purity is more than or equal to 99.999%) of 2cm is put into acetone and soaked 20 minutes, with cotton balls with its surperficial wiped clean, and use deionized water rinsing, using volume ratio is 1: 4 perchloric acid and alcohol mixed solution electrochemical etching under constant-pressure conditions.Using low temperature thermostat bath electrolyte temperature to be reduced to-6 ℃, is that 195V, current density be 2000mA/m with aluminium flake at anode voltage by the mixer means of routine
2Condition corroded 3 minutes next time.Is to soak 2 hours in 60 ℃ phosphoric acid (6wt.%) and chromic acid (1.8wt.%) mixed aqueous solution the sample after the corrosion once in temperature, to remove the once aluminum oxide of corrosion generation.With once corrode identical condition under, sample was carried out anticaustic 10 minutes.The multiaperture pellumina of preparing is the hexagonal solid matter each other and distributes between the surface tissue unit, the hole distribution height is orderly, and the aperture is 90nm, and pitch of holes is 360nm, and barrier layer thickness is 140nm, and film thickness is about 50 μ m.
Embodiment 3
Electrolytic solution is by H
2O, C
2H
5OH and H
3PO
4Formulated, H wherein
2O and C
2H
5The OH volume ratio is 4: 1, H
3PO
4Content is 0.5mol/L, and the electrolytic solution cumulative volume is 2L.With diameter is that the circular aluminium flake (purity is more than or equal to 99.999%) of 2cm is put into acetone and soaked 20 minutes, with cotton balls with its surperficial wiped clean, and use deionized water rinsing, using volume ratio is 1: 4 perchloric acid and alcohol mixed solution electrochemical etching under constant-pressure conditions.Using low temperature thermostat bath electrolyte temperature to be reduced to-10 ℃, is that 195V, current density be 4000mA/m with aluminium flake at anode voltage by the mixer means of routine
2Condition corroded 2 minutes next time.Is to soak 3 hours in 60 ℃ phosphoric acid (6wt.%) and chromic acid (1.8wt.%) mixed aqueous solution the sample after the corrosion once in temperature, to remove the once aluminum oxide of corrosion generation.With once corrode identical condition under, sample was carried out anticaustic 10 minutes.The multiaperture pellumina of preparing is the hexagonal solid matter each other and distributes between the surface tissue unit, the hole distribution height is orderly, and the aperture is 120nm, and pitch of holes is 320nm, and barrier layer thickness is 120nm, and film thickness is about 100 μ m.
Claims (8)
1, a kind of fast stable growth process of alumina film with nanometer pore array of relatively great pore distance is characterized in that, concrete steps are:
The first, preparation phosphoric acid-water-ethanol electrolytic solution: H wherein
2O and C
2H
5The OH volume ratio is 4: 1, H
3PO
4Concentration is 0.25-0.5mol/L, and the electrolytic solution cumulative volume is 2L;
The second, aluminium flake pre-treatment: circular aluminium flake is put into acetone soak,, and use deionized water rinsing, use perchloric acid and alcohol mixed solution electrochemical etching under constant-pressure conditions with its surperficial wiped clean;
The 3rd, use low temperature thermostat bath electrolyte temperature to be reduced to-5～-10 ℃ of temperature, and electrolytic solution is stirred, be that 195V, current density are 1500-4000Am at anodic oxidation voltage
-2Condition under aluminium flake is once corroded;
The 4th, the sample after once corroding to be soaked in the chromic acid mixed aqueous solution, temperature remains on 60 ℃, to remove the aluminum oxide that once corrosion produces;
The 5th, under the condition identical, sample is carried out anticaustic with the 3rd step.
2, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, described circular aluminium flake, its diameter are 2cm, adopts purity more than or equal to 99.999% aluminium flake.
3, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, in second step, and described immersion, the time is 20 minutes.
4, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, described perchloric acid and alcohol mixed solution, and perchloric acid and ethanol volume ratio are 1: 4.
5, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, described once corrosion, and the time is 2～5 minutes.
6, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, in the 4th step, and described immersion, the time is 2～4 hours.
7, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, described phosphoric acid and chromic acid mixed aqueous solution, and wherein the weight percent of phosphoric acid and chromic acid is respectively 6% and 1.8%.
8, the fast stable growth process of the alumina film with nanometer pore array of relatively great pore distance according to claim 1 is characterized in that, described anticaustic, and the time is within ten minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147108A (en) * | 2013-03-14 | 2013-06-12 | 山西师范大学 | Anodic aluminum oxide film and preparation method thereof |
| CN103243370A (en) * | 2013-04-25 | 2013-08-14 | 东华大学 | Method for preparing ordered macroporous anodic alumina film by two-step anodic oxidation |
| CN105543931A (en) * | 2016-01-13 | 2016-05-04 | 西安交通大学 | Aluminium alloy based surface dimension adjustable nanopore array and quick preparation method thereof |
| CN105887156A (en) * | 2013-05-17 | 2016-08-24 | 江苏理工学院 | Preparation method of highly ordered porous anodic aluminum oxide film |
| CN114277419A (en) * | 2021-12-09 | 2022-04-05 | 广东工业大学 | Large-pore-spacing anodic aluminum oxide film based on parabolic equation boosting and preparation method and application thereof |
-
2006
- 2006-11-23 CN CN 200610118666 patent/CN1974873A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147108A (en) * | 2013-03-14 | 2013-06-12 | 山西师范大学 | Anodic aluminum oxide film and preparation method thereof |
| CN103147108B (en) * | 2013-03-14 | 2016-03-16 | 山西师范大学 | A kind of anodic alumina films and preparation method thereof |
| CN103243370A (en) * | 2013-04-25 | 2013-08-14 | 东华大学 | Method for preparing ordered macroporous anodic alumina film by two-step anodic oxidation |
| CN103243370B (en) * | 2013-04-25 | 2015-12-23 | 东华大学 | A kind of two step anonizings prepare the method for ordered big hole anodic aluminum oxide film |
| CN105887156A (en) * | 2013-05-17 | 2016-08-24 | 江苏理工学院 | Preparation method of highly ordered porous anodic aluminum oxide film |
| CN105543931A (en) * | 2016-01-13 | 2016-05-04 | 西安交通大学 | Aluminium alloy based surface dimension adjustable nanopore array and quick preparation method thereof |
| CN114277419A (en) * | 2021-12-09 | 2022-04-05 | 广东工业大学 | Large-pore-spacing anodic aluminum oxide film based on parabolic equation boosting and preparation method and application thereof |
| CN114277419B (en) * | 2021-12-09 | 2023-05-23 | 广东工业大学 | Macroporous-spacing anodic aluminum oxide film based on parabolic equation boosting and preparation method and application thereof |
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