CN102839408A - Method for preparing porous aluminum oxide film with super-large hole pitch through ultrasonic auxiliary anode oxidation - Google Patents
Method for preparing porous aluminum oxide film with super-large hole pitch through ultrasonic auxiliary anode oxidation Download PDFInfo
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- CN102839408A CN102839408A CN2012102829922A CN201210282992A CN102839408A CN 102839408 A CN102839408 A CN 102839408A CN 2012102829922 A CN2012102829922 A CN 2012102829922A CN 201210282992 A CN201210282992 A CN 201210282992A CN 102839408 A CN102839408 A CN 102839408A
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Abstract
The invention relates to a porous anode aluminum oxide film and especially relates to a method for preparing a porous aluminum oxide film with a super-large hole pitch through ultrasonic auxiliary anode oxidation. According to the method, alcohol is added into a citric acid electrolyte so as to increase an electrolytic voltage, and an ultrasonic technique is combined for increasing the electrolytic rate so as to realize ultrahigh voltage (more than 500V) stable electrolysis and obtain the PAA with the super-large hole pitch exceeding 1 micron. According to the method, only the secondary anodic oxidation technology is required, no rigorous demand on the pretreatment of aluminum sheets exists, and the complex pretreatment steps of annealing, polishing or pre-patterning are not required. According to the method, during the electrolytic process, the ultralow temperature required by hard anodizing is not required and the film can stably grow within an ultra-wide temperature range (0-30 DEG C).
Description
Technical field
The present invention relates to porous anodic alumina films; Refer in particular to ultrasonic supplementary anode oxidation and prepare the method for oversized hole spacing multiaperture pellumina; Belong to metal surface treatment technology and nanosecond science and technology field, its Application Areas includes non-ferrous metal surface treatment and the preparation of nanostructure novel material and uses.
Background technology
Porous anodic aluminium oxide, Porous Anodic Alumina, PAA, not only extremely important to the aluminum metal surface treatment, also be simultaneously the important template of nano structural material preparation and assembling; The PAA typical structure is the circular port periodic arrangement, forms nano-pore array structure, and the hole wall between the Kong Yukong is made up of amorphous nickel/phosphorus/aluminium oxide; The pore size of PAA is a very important parameter; Such as as filtering membrane time decision hold back the size of object; Determine the yardstick of prepared nano material when using, the pore size of the PAA that anodic oxidation obtains and electrolysis voltage, parameter correlations such as temperature and time as template.The further reaming of phosphoric acid can be passed through in the aperture of PAA, is about 10 nanometers up to hole wall; As, in 0.3M oxalic acid, electrolysis voltage is 40 V, electrolysis temperature is 0-5
oUnder the C, the PAA template initial aperture that anodic oxidation obtains is 40 nm, and the initial apertures spacing is 100 nm; Through control phosphoric acid reaming process, the aperture can change to 90 nm from 40 nm continuously, and pitch of holes is constant; Therefore, the pitch of holes of PAA has determined the adjustable extent in PAA aperture.
The pitch of holes of PAA mainly is by the electrolysis voltage decision, and presents linear proportional relation basically with electrolysis voltage, and the pitch of holes that therefore will improve PAA mainly is to improve electrolysis voltage; In 3 wt% phosphoric acid solutions, electrolysis voltage can be brought up under 195 V, in 1 vol% phosphoric acid solution, and 273 K, electrolysis voltage can be brought up to 235 V, obtains the PAA film of 480 nm pitchs of holes; In the solution of 4 wt% oxysuccinic acid, electrolysis voltage is 220 V, and the pitch of holes of acquisition is about the PAA film of 550 nm; 240 V in 2 wt% tartaric acid solutions obtain the PAA film of about 600 nm of average pitch of holes under 274 K.In Hydrocerol A electrolytic solution, electrolysis voltage can reach 240 V.
A large amount of experiments show, though in weak acid such as Hydrocerol A and oxysuccinic acid, can electrolysis voltage be risen to more than 200 V, rise to 300 V even higher very difficulty, and growth velocity are very low; 40V electrolysis voltage in 0.3M oxalic acid, 0-5 degree centigrade, the growth velocity of PAA is 3-5 μ m/h, but corresponding growth velocity has only 1-2 μ m/h in electrolytic solution such as Hydrocerol A and oxysuccinic acid; In electrolytic solution, add ethanol, terepthaloyl moietie, or polyoxyethylene glycol can further improve electrolysis voltage, but with respect to not adding organic electrolytic solution, the growth velocity of PAA is lower; Therefore, need seek a kind ofly can under extra-high pressure, stablize electrolysis and the moderate PAA preparation technology of growth velocity, further widen the pitch of holes size of PAA.
Summary of the invention
(the current electrolysis under voltage can get at the PAA of micron to many deficiencies of the oversized hole spacing PAA technology that the present invention is directed in the technical background to be set forth with the preparation aperture; And the growth velocity of PAA is lower etc.); Use is added ethanol and is improved electrolysis voltage in Hydrocerol A electrolytic solution; Improve electrolysis speed in conjunction with ultrasonic technology, and realize extra-high pressure (>500V) stablize electrolysis, and obtain the oversized hole spacing PAA that pitch of holes surpasses 1 micron; The present invention only needs two-step anodization technology, and pre-treatment does not have harsh requirement to aluminium flake, does not need complicated annealing, pre-treatment steps such as polishing or preparatory patterning; The present invention need not need extremely low temperature, (0-30 in very wide TR as hard anodizing (Hard Anodization) in electrolytic process
oC) can both carry out stable growth.
To achieve these goals; The present invention realizes the preparation of oversized hole spacing PAA through following technical scheme: the first step is an anode with the aluminium flake, the mixed electrolytic solution of configuration citric acid solution and absolute ethyl alcohol; Make electrolytic solution be in ultrasonic state, electrolysis time 0.5-2 hour; Second step: in the mixing solutions of phosphoric acid and chromic acid, remove the PAA film; The 3rd step: electrolyte system, electrolysis voltage and temperature are identical with the first step, and electrolysis time hole depth is as required confirmed.
The described the first step, aluminium flake are meant that specifically purity is higher than 99 %, and thickness is the aluminium flake of 0.05-1 mm, are negative electrode as anode with graphite, stereotype or platinum through oven dry after acetone and the washed with de-ionized water; The volume ratio of Hydrocerol A and absolute ethyl alcohol is 1:1 ~ 2, and the concentration of Hydrocerol A is 0.3M, and ultrasonic power and frequency are respectively 100-200 W and 35 ~ 50kHz, and electrolysis voltage is 500-750 V, and electrolysis temperature is 0-30
oC, electrolysis time are 0.5-2h.
In described second step, in phosphoric acid and the chromic acid mixing solutions, the weight percent of phosphoric acid is 6.0 %, and the weight percent of chromic acid is 1.8 %, and temperature is 60
oC soaks the twice for the first step electrolysis time, i.e. 1-4 h.
In described the 3rd step, electrolysis voltage is identical with the first step, the thickness of electrolysis time decision PAA film, and typical electrolysis time is 5 minutes to 2 hours.
By the method for above-mentioned ultrasonic aid preparation oversized hole spacing anodic alumina films, the oversized hole spacing of preparation is 1-1.5 μ m.
By the method for above-mentioned ultrasonic aid preparation oversized hole spacing anodic alumina films, growth velocity reaches 4-60 μ m/h.
Method by above-mentioned ultrasonic aid preparation oversized hole spacing anodic alumina films; Electrolytic process stability is higher for the first time with for the second time; N.s. burns (electric field is concentrated the Burning phenomenon that causes), and the PAA growth velocity has increase slightly along with the raising of electrolyte temperature.
By the method for above-mentioned ultrasonic aid preparation oversized hole spacing anodic alumina films, the growth velocity of PAA film increases along with the raising of electrolysis voltage.
By the method for above-mentioned ultrasonic aid preparation oversized hole spacing anodic alumina films, the PAA film thickness of preparation increases and increases along with electrolysis time.
The method of ultrasonic aid preparation oversized hole spacing anodic alumina films of the present invention, the growth velocity of PAA film is relevant with ultrasonic power, and ultrasonic power increases, and the PAA layer-growth rate has increase slightly.
Can know by technique scheme, the method for ultrasonic aid preparation oversized hole spacing anodic alumina films of the present invention, comparing the advantage that has with existing general technology has: 1, electrolysis voltage rises to 500-750V; 2, pitch of holes is 1-1.5 μ m; 3, the stable electrolysis process and the temperature window of broad; 4, avoided the pre-treating technology such as high temperature annealing and chemical rightenning of aluminium; Therefore; The method of ultrasonic aid preparation oversized hole spacing anodic alumina films described in the invention is a kind of PAA preparation method with using value of simple, efficient and easy care; The pore diameter range that can expand PAA is to 1000-1500 nm; Realize the combination of nanoscale aperture and micro-meter scale aperture nanostructure, and can be used in the PAA film of micron-nanometer composite structure, and further be applied to the preparation of micro-nanometer structural material.
Description of drawings
Fig. 1 is the cross section sem photograph of embodiment 1 sample;
Fig. 2 is the surface scan Electronic Speculum figure of embodiment 1 sample;
Fig. 3 is the surface scan Electronic Speculum figure after the reaming of embodiment 1 sample;
Fig. 4 is the cross section sem photograph of embodiment 2 samples;
Fig. 5 is the cross section sem photograph of embodiment 3 samples;
Fig. 6 is the cross section sem photograph of embodiment 4 samples;
Fig. 7 is the surface scan Electronic Speculum figure of embodiment 4 samples.
Embodiment
Further specify content of the present invention below in conjunction with instance:
Case one:
The first step is with purity 99.999% thickness 100 μ m areas 4 cm
2High-purity aluminum foil, in acetone, soaked 2 minutes, acetone rinsing is dried behind the deionized water rinsing, puts into electrolyzer as anode; Graphite Electrodes, area are 200 cm
2It is the Hydrocerol A of 0.3 M and the ethanol of 2 L that electrolytic solution consists of 1 L concentration, and electrolyte temperature uses the circularly cooling machine to be stabilized in 0-5
oC, electrolysis voltage 750 V, ultrasonic power 100 W, frequency 35 kHz, electrolysis time 30 minutes.
In second step, in chromic acid, soaked 1 hour.
In the 3rd step, electrolysis is 10 minutes under the processing condition identical with step 1.
The cross section structure of gained sample is as shown in Figure 1, and the surface is as shown in Figure 2; From the cross section, each hole all is positioned at the unitary mid-way of U type.The hole between centers is about 1.5 microns; Obtain 100 nm pitchs of holes with electrolysis under 0.3 M oxalic acid, 40 V and keep identical electrolysis voltage-pitch of holes relation; About 1.5 microns of hole depths; Growth velocity reaches 9 μ m/h, is higher than general PAA growth velocity (0.3M oxalic acid 40V, typical growth speed is 3-5 μ m/h); Different with general PAA is; The oversized hole spacing PAA hole inwall that the present invention obtained not is smooth or vertical, and this shows as the not too hole shape looks of rule in surperficial Photomicrograph, but for the duct that utilizes PAA; The imperfect use that does not influence the duct on surface; On the contrary, when material was filled in such PAA duct, rough duct helped to obtain different structure.
The sample that is obtained is put into 5wt% phosphoric acid, 30 degrees centigrade, soaked 10 hours, surface topography is as shown in Figure 3, and the aperture of PAA greatly increases, and pitch of holes does not change, and this result shows that the PAA aperture that the present invention obtains can reach more than 1 micron.
Case row two:
The first step is with purity 99.999 % thickness 100 μ m areas 4 cm
2High-purity aluminum foil, in acetone, soaked 2 minutes, acetone rinsing is dried behind the deionized water rinsing, puts into electrolyzer as anode.Graphite Electrodes, area are 200 cm
2Electrolytic solution consists of 0.3 M Hydrocerol A, 1 L and 1.5 L ethanol, and electrolyte temperature uses the circularly cooling machine to be stabilized in 15
oC, electrolysis voltage 600 V, ultrasonic power 150 W, frequency 50 kHz, electrolysis time 30 minutes.
In second step, in chromic acid, soaked 1 hour.
In the 3rd step, electrolysis is 20 minutes under the processing condition identical with step 1.
The cross section structure of gained sample is as shown in Figure 4.The hole between centers is about 1.2 μ m; Obtain 100 nm pitchs of holes with electrolysis under the 0.3M oxalic acid 40V and keep identical electrolysis voltage-pitch of holes relation, about hole depth 7 μ m, growth velocity reaches 21 μ m/h; Far above general PAA growth velocity (0.3 M oxalic acid, 40 V; Typical growth speed is 3-5 μ m/h), different with general PAA is that the duct is not to be parallel to each other fully.
Case row three:
The first step is with purity 99.999 % thickness 100 μ m areas 4 cm
2High-purity aluminum foil, in acetone, soaked 2 minutes, acetone rinsing is dried behind the deionized water rinsing, puts into electrolyzer as anode, Graphite Electrodes, area are 200cm
2Electrolytic solution consists of 0.3M Hydrocerol A 1 L and 1 L ethanol.Electrolyte temperature uses the circularly cooling machine to be stabilized in 30
oC, electrolysis voltage 500 V, ultrasonic power 200W, frequency 45 kHz, electrolysis time 60 minutes.
In second step, in chromic acid, soaked 2 hours.
In the 3rd step, electrolysis is 30 minutes under the processing condition identical with step 1.
The cross section structure of gained sample is as shown in Figure 5, and the hole between centers is about 1 μ m, obtains 100 nm pitchs of holes with electrolysis under 0.3 M oxalic acid, 40 V and keeps identical electrolysis voltage-pitch of holes relation; About hole depth 12 μ m, growth velocity reaches 24 μ m/h, far above general PAA growth velocity (0.3 M oxalic acid, 40 V; Typical growth speed is 3-5 μ m/h); Different with general PAA is that the duct is not to be parallel to each other fully, and hole wall and rough or vertical.
Comparative Examples four:With case one contrast
The first step is with purity 99.999 % thickness 100 μ m areas 4 cm
2High-purity aluminum foil, in acetone, soaked 2 minutes, acetone rinsing is dried behind the deionized water rinsing, puts into electrolyzer as anode, Graphite Electrodes, area are 200 cm
2Electrolytic solution consists of 0.3 M Hydrocerol A, 1 L and 2 L ethanol, and electrolyte temperature uses the circularly cooling machine to be stabilized in 0-5
oC, electrolysis voltage 750 V, do not have ultrasonic, electrolysis time 30 min.
In second step, in chromic acid, soak 1 h.
The 3rd step, electrolysis 10 min under the processing condition identical with step 1.
The surface of gained sample and cross section are shown in Fig. 6 and 7; From surperficial Photomicrograph, can see distribute not specification and the very low pore structure of fraction of coverage; From the cross section, any pore structure is almost can't see in each hole, the thickness of oxide layer that forms also only about 200 nm; Shown in black arrow among Fig. 6,1.5 μ m hole depths in the case one.These results compare with case one, show ultrasonicly to play crucial effects in the present invention, if in electrolytic process, do not have ultrasonicly just can't obtain PAA pore passage structure preferably, and zone of oxidation to form speed very low.
Comparative Examples five: with case two contrasts
The first step is with purity 99.999 % thickness 100 μ m areas 4 cm
2High-purity aluminum foil, in acetone, soaked 2 minutes, acetone rinsing is dried behind the deionized water rinsing, puts into electrolyzer as anode, Graphite Electrodes, area are 200 cm
2Electrolytic solution consists of 0.3 M Hydrocerol A, 1 L and 1.5 L ethanol, and electrolyte temperature uses the circularly cooling machine to be stabilized in 15
oC, electrolysis voltage 600V, ultrasonic power 300 W, frequency 20 kHz, electrolysis time 30 min.
In second step, in chromic acid, soak 1 h.
The 3rd step, electrolysis 20 min under the processing condition identical with step 1.
The surface of gained sample and cross section are similar to shown in Fig. 6 and 7 of Comparative Examples 4; These results compare with case 2; The selection of ultransonic power and frequency plays crucial effects in the present invention; The selection of ultrasonic power and frequency just can't not obtain PAA pore passage structure preferably in scope of the present invention in electrolytic process, and zone of oxidation formation speed is very low.
Claims (6)
1. ultrasonic supplementary anode oxidation prepares the method for oversized hole spacing multiaperture pellumina, it is characterized in that comprising the steps:
(1) with the aluminium flake be anode, the mixed electrolytic solution of configuration citric acid solution and absolute ethyl alcohol makes electrolytic solution be in ultrasonic state, electrolysis time 0.5-2 hour; (2) in the mixing solutions of phosphoric acid and chromic acid, remove the PAA film; (3) electrolyte system, electrolysis voltage and temperature are identical with the first step, and electrolysis time hole depth is as required confirmed.
2. ultrasonic supplementary anode oxidation as claimed in claim 1 prepares the method for oversized hole spacing multiaperture pellumina; It is characterized in that: described step (1); Aluminium flake is meant that specifically purity is higher than 99 %; Thickness is the aluminium flake of 0.05-1 mm, and through acetone and washed with de-ionized water, is negative electrode with graphite, stereotype or platinum; The volume ratio of Hydrocerol A and absolute ethyl alcohol is 1:1 ~ 2, and the concentration of Hydrocerol A is 0.3M, and ultrasonic power and frequency are respectively 100-200 W and 35 ~ 50kHz, and electrolysis voltage is 500-750 V, and electrolysis temperature is 0-30
oC, electrolysis time are 0.5-2h.
3. ultrasonic supplementary anode oxidation as claimed in claim 1 prepares the method for oversized hole spacing multiaperture pellumina; It is characterized in that: described step (2), in phosphoric acid and the chromic acid mixing solutions, the weight percent of phosphoric acid is 6.0 %; The weight percent of chromic acid is 1.8 %, and temperature is 60
oC, soak time is the twice of the first step electrolysis time, i.e. 1-4 h.
4. ultrasonic supplementary anode oxidation as claimed in claim 1 prepares the method for oversized hole spacing multiaperture pellumina, it is characterized in that: described step (3), electrolysis time are 5 minutes to 2 hours.
5. ultrasonic supplementary anode oxidation as claimed in claim 1 prepares the method for oversized hole spacing multiaperture pellumina, it is characterized in that: said oversized hole spacing is 1-1.5 μ m.
6. ultrasonic supplementary anode oxidation as claimed in claim 1 prepares the method for oversized hole spacing multiaperture pellumina, it is characterized in that: growth velocity reaches 4-60 μ m/h.
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Cited By (3)
| 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 |
| CN106544712A (en) * | 2016-10-19 | 2017-03-29 | 陕西师范大学 | A kind of orderly super large pitch of holes pellumina and preparation method thereof |
| CN106670744A (en) * | 2016-12-21 | 2017-05-17 | 西安理工大学 | Method for preparing wear-resisting dewatering slippage functional film on inner surface of bearing bush |
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Cited By (6)
| 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 |
| CN106544712A (en) * | 2016-10-19 | 2017-03-29 | 陕西师范大学 | A kind of orderly super large pitch of holes pellumina and preparation method thereof |
| CN106544712B (en) * | 2016-10-19 | 2019-06-07 | 陕西师范大学 | A kind of preparation method of orderly super large pitch of holes pellumina |
| CN106670744A (en) * | 2016-12-21 | 2017-05-17 | 西安理工大学 | Method for preparing wear-resisting dewatering slippage functional film on inner surface of bearing bush |
| CN106670744B (en) * | 2016-12-21 | 2018-09-25 | 西安理工大学 | A kind of preparation method of the wear-resisting hydrophobic sliding functional membrane of inner surface of bearing bush |
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Effective date of registration: 20210601 Address after: 213002 No.26, Zhufeng Road, Xinbei District, Changzhou City, Jiangsu Province Patentee after: Changzhou APU Intelligent Technology Co.,Ltd. Address before: 213164 Changzhou University, 1 Hu Hu Road, Wujin District, Changzhou, Jiangsu Patentee before: CHANGZHOU University |