CN102181901A - Method for preparing alumina membrane with adjustable color and high saturation - Google Patents
Method for preparing alumina membrane with adjustable color and high saturation Download PDFInfo
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- CN102181901A CN102181901A CN 201110082333 CN201110082333A CN102181901A CN 102181901 A CN102181901 A CN 102181901A CN 201110082333 CN201110082333 CN 201110082333 CN 201110082333 A CN201110082333 A CN 201110082333A CN 102181901 A CN102181901 A CN 102181901A
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Abstract
The invention discloses a method for preparing an alumina membrane with adjustable color and high saturation. The method is mainly a reoxidation method, and the oxidation is carried out in 0.3mol/L solution of oxalic acid; when the voltage and the temperature are constant, the color of the anodic alumina membrane is controlled by adjusting the secondary oxidation time, and the color saturation of the membrane is improved by peeling an aluminum base. Simple patterns are prepared by an organic matter-aided method. The alumina membrane has a bright color, and alumina membranes in various colors and with different simple patterns can be prepared by adjustment. The pollution brought by dyes and pigments can be lightened by the method and the method has the characteristics of simple operation, low carbon and environmental friendliness.
Description
Technical field
The present invention relates to a kind of color tunable and have the preparation method of the aluminum oxide film of high saturation, belong to the optical material preparing technical field.
Background technology
Schemochrome has a wide range of applications in biology, and some have the structure (as the feathers of birds and butterfly's wing etc.) of the interference of light occurring in nature, chromatic colour is not only arranged, and can change with the difference of people's viewing angle.Schemochrome is producing interference of light with the comparable periodic micro structure of visible wavelength and causing of having owing to object.Optical interference structures has wide practical use at colour display screen, decoration and field such as false proof.According to the researchist of the Chinese Academy of Sciences, because the ultrafine orderly anodic aluminum oxide film of aluminium base porous that has of interference of light can produce distinct colors under natural light, yet this color saturation is relatively poor recently.For purity and the saturation ratio thereof that improves color, the researchist inlays carbon nanotube having on the aluminium base anodic aluminum oxide film.It should be noted that the aluminium base of all unstripped aluminum oxide of the above experiment back side, this has limited the application of anodised aluminium in microdevices such as color display greatly.
Summary of the invention
The purpose of this invention is to provide a kind of color tunable and have the preparation method of the aluminum oxide film of high saturation, solved complicated process of preparation, preparation cost height in the past, and can not control technical problems such as color well.
The technical scheme that the present invention takes is such:
A kind of color tunable and have the preparation method of the aluminum oxide film of high saturation may further comprise the steps:
(1) be that high-purity aluminium flake of 99.999% places tube furnace with purity, 500 ℃ are adopted argon gas to do shielding gas down, and anneal 2.5h is to eliminate the stress of aluminium flake inside;
(2) aluminium flake after the anneal is put in the acetone soln, carries out ultrasonic cleaning 15min, again aluminium flake is carried out electropolishing and handle 5min, clean and remove the polishing fluid on aluminium flake surface, dry in order to anodic oxidation used then to remove the grease on the aluminium flake;
(3) aluminium flake and copper electrode are fixed on the anode of electrolyzer, adding concentration then in electrolyzer is the oxalic acid electrolytic solution of 0.3mol/L, the copper electrode that aluminium flake is housed is linked to each other with the positive pole of direct supply, graphite rod links to each other with the negative pole of direct supply, be separately fixed at the electrolyzer two ends, carry out the oxidation first time, anodic oxidation voltage is 45V for the first time, temperature is controlled at 5 ℃, and oxidization time is 6h;
(4) rinse well with the alumina formwork that obtains after the deionized water oxidation for the first time, then alumina formwork is put into and be respectively the mixed acid solution that the chromic acid of the phosphoric acid of 70g/L and 35g/L mixed in 1: 1 by volume by concentration and remove the pellumina that oxidation obtains through the first time, carry out the oxidation second time then, concrete operations are as follows: adding concentration in the electrolyzer is the oxalic acid solution of 0.3mol/L, oxidation voltage is 45V for the second time, temperature is controlled at 5 ℃, and oxidization time is 90～160s for the second time;
(5) after anodic oxidation is for the second time finished, remove the aluminium base of the pellumina back side, obtain the aluminum oxide film of the different colours formed by porous layer and blocking layer at last with saturated Cupric Chloride Solution.
Above-mentioned preparation method, in the step (4), when the second time, oxidization time was 90s, aluminum oxide film showed purple.
Above-mentioned preparation method, in the step (4), when the second time, oxidization time was 100s, aluminum oxide film showed blue.
Above-mentioned preparation method, in the step (4), when the second time, oxidization time was 110s, aluminum oxide film showed blue-greenish colour.
Above-mentioned preparation method, in the step (4), when the second time, oxidization time was 120s, aluminum oxide film showed green.
Above-mentioned preparation method, in the step (4), when the second time, oxidization time was 140s, aluminum oxide film showed orange.
Above-mentioned preparation method, in the step (4), when the second time, oxidization time was 160s, aluminum oxide film showed red.
The beneficial effect that the present invention obtains is, preparation technology is simple, easy handling, can control the film color by the controlled oxidation time, and the saturation ratio of film color increases obviously, prepared product can substitute industrial widely used dyestuff, pigment, pollute thereby reduce, low-carbon environment-friendly, and can arbitrarily make the simple pattern of various demonstration different colours can be used for colour display screen, decoration and field such as false proof.
Description of drawings
Fig. 1 is the oxidation different time and remove aluminium base rear oxidation aluminium film photo under natural light for the second time according to the present invention.
Fig. 2 is the oxidation different time and remove aluminium base rear oxidation aluminium film uv-vis spectra for the second time according to the present invention.
Fig. 3 shows the SEM surface and the sectional view of the aluminum oxide film of the embodiment of the invention 1.
Fig. 4 removes aluminium base back photo under natural light according to the present invention for an aluminum oxide film oxidation different time.
Fig. 5 shows the schematic diagram that the present invention removes aluminium base front and back.
Fig. 6 is a simple pattern prepared in accordance with the present invention.
Embodiment
Following specific embodiment is used to illustrate the present invention.It may be noted that these embodiment only are used to illustrate the present invention, rather than limit the scope of the invention.
It is the preparation of blue-greenish colour anodic aluminum oxide film that embodiment 1 removes aluminium base back
(1) high-purity aluminium flake (purity 99.999%) is placed 500 ℃ of following anneal 2.5h of tube furnace, adopt argon gas to do shielding gas, to eliminate the stress of aluminium flake inside;
(2) aluminium flake after the anneal is put in the acetone soln, carries out ultrasonic cleaning 15min, at last aluminium flake is carried out electropolishing and handle 5min, clean and remove the polishing fluid on aluminium flake surface, dry in order to anodic oxidation used then to remove the grease on the aluminium flake;
(3) aluminium flake and copper electrode are fixed on the anode of electrolyzer, adding 400ml concentration then in electrolyzer is the oxalic acid electrolytic solution of 0.3mol/L, the copper electrode that aluminium flake is housed is linked to each other with the positive pole of direct supply, graphite rod links to each other with the negative pole of direct supply, carry out the oxidation first time, oxidation voltage is 45V for the first time, and temperature is controlled at 5 ℃, and oxidization time is 6h;
(4) rinse well with the alumina formwork that obtains after the deionized water oxidation for the first time, then alumina formwork is put into mixed acid solution (concentration is respectively the phosphoric acid of 70g/L and the chromic acid of 35g/L mixed in 1: 1 by volume), removed the pellumina that oxidation obtains through the first time.Carry out the oxidation second time then, concrete operations are as follows: adopting 400ml concentration is the oxalic acid solution of 0.3mol/L, and oxidation voltage is 45V for the second time, and temperature is controlled at 5 ℃, and oxidization time is 110s for the second time;
(5) utilize saturated CuCl
2It is aluminium base to remove the pellumina back side, is glaucous anodic aluminum oxide film thereby obtain removing aluminium base back.
Adopt Sony Dsc-T20 digital camera that aluminum oxide film is taken, the gained photo is shown in Fig. 1 (c), and the centre of film has been peeled off the aluminium base blue-greenish colour that is among the figure, and does not remove aluminium base taking on a red color on every side, both complementary colors, but the former color saturation is higher.
Use Hitachi UV-3010 uv-vis spectra that above-mentioned film is analyzed, it the results are shown among Fig. 2, and it maximum value occurs when 500nm.
Use Hitachi S-570 scanning electronic microscope that above-mentioned film is observed, observe its surface and sectional view respectively, it the results are shown among Fig. 3, can see that its hole queueing discipline and film thickness are about 240nm.
Fig. 5 is the schematic diagram of the interference of light of the aluminium base front and back of removal, can illustrate and remove aluminium base influence the film color, it is mutually identical that upper and lower surface reflects formed two coherent light positions among a, no extra half-wave path difference, promptly disregard half-wave loss, according to formula 2ndcos θ=j λ, n=1.57 (calculating gained) vertical incidence cos θ=1 wherein, it is mutually opposite that d=240nm, j=1 can calculate the two coherent light positions that interfere among λ=753.6nm (redness) b, has half-wave loss, according to λ/2 of formula 2ndcos θ=(2j+1), d=240nm wherein, j=1 can calculate λ=502.4nm (blue-greenish colour), so color changes.
It is the preparation of orange anodic aluminum oxide film that embodiment 2 removes aluminium base back
(1) high-purity aluminium flake (purity 99.999%) is placed 500 ℃ of following anneal 2.5h of tube furnace, adopt argon gas to do shielding gas, to eliminate the stress of aluminium flake inside;
(2) aluminium flake after the anneal is put in the acetone soln, carries out ultrasonic cleaning 15min, at last aluminium flake is carried out electropolishing and handle 5min, clean and remove the polishing fluid on aluminium flake surface, dry in order to anodic oxidation used then to remove the grease on the aluminium flake;
(3) aluminium flake and copper electrode are fixed on the anode of electrolyzer, adding 400ml concentration then in electrolyzer is the oxalic acid electrolytic solution of 0.3mol/L.The copper electrode that aluminium flake is housed is linked to each other with the positive pole of direct supply, and graphite rod links to each other with the negative pole of direct supply, carries out the oxidation first time, and oxidation voltage is 45V for the first time, and temperature is controlled at 5 ℃, and oxidization time is 6h;
(4) rinse well with the alumina formwork that obtains after the deionized water oxidation for the first time, then alumina formwork is put into mixed acid solution (concentration is respectively the phosphoric acid of 70g/L and the chromic acid of 35g/L mixed in 1: 1 by volume), removed the pellumina that oxidation obtains through the first time.Carry out the oxidation second time then, concrete operations are as follows: adopting 400ml concentration is the oxalic acid solution of 0.3mol/L, and oxidation voltage is 45V for the second time, and temperature is controlled at 5 ℃, and oxidization time is 140s for the second time;
(5) utilize saturated CuCl
2It is aluminium base to remove the pellumina back side, is orange anodic aluminum oxide film thereby obtain removing aluminium base back.
Adopt Sony Dsc-T20 digital camera that aluminum oxide film is taken, the gained photo is shown in Fig. 1 (e).
Use Hitachi UV-3010 uv-vis spectra that above-mentioned film is analyzed, it the results are shown among Fig. 2, and it maximum value occurs when 620nm.
It is the preparation of red anodic aluminum oxide film that embodiment 3 removes aluminium base back
(1) high-purity aluminium flake (purity 99.999%) is placed 500 ℃ of following anneal 2.5h of tube furnace, adopt argon gas to do shielding gas, to eliminate the stress of aluminium flake inside.
(2) aluminium flake after the anneal is put in the acetone soln, carries out ultrasonic cleaning 15min, at last aluminium flake is carried out electropolishing and handle 5min, clean and remove the polishing fluid on aluminium flake surface, dry in order to anodic oxidation used then to remove the grease on the aluminium flake;
(3) aluminium flake and copper electrode are fixed on the anode of electrolyzer, adding 400ml concentration then in electrolyzer is the oxalic acid electrolytic solution of 0.3mol/L, the copper electrode that aluminium flake is housed is linked to each other with the positive pole of direct supply, graphite rod links to each other with the negative pole of direct supply, carry out the oxidation first time, oxidation voltage is 45V for the first time, and temperature is controlled at 5 ℃, and oxidization time is 6h;
(4) rinse well with the alumina formwork that obtains after the deionized water oxidation for the first time, then alumina formwork is put into mixed acid solution (concentration is respectively the phosphoric acid of 70g/L and the chromic acid of 35g/L mixed in 1: 1 by volume), remove the pellumina that oxidation obtains through the first time, carry out the oxidation second time then, concrete operations are as follows: adopting 400ml concentration is the oxalic acid solution of 0.3mol/L, oxidation voltage is 45V for the second time, and temperature is controlled at 5 ℃, and oxidization time is 160s for the second time;
(5) utilize saturated CuCl
2It is aluminium base to remove the pellumina back side, is red anodic aluminum oxide film thereby obtain removing aluminium base back.
Adopt Sony Dsc-T20 digital camera that the aluminium base back of the removal of preparation is taken for red AAO film, the gained photo is shown in Fig. 1 (f).
Use Hitachi UV-3010 uv-vis spectra that above-mentioned film is analyzed, it the results are shown among Fig. 2, and it maximum value occurs when 710nm.
The preparation of the pattern of forming by different colours on the case study on implementation 4 same aluminum oxide films
(1) high-purity aluminium flake (purity 99.999%) is placed 500 ℃ of following anneal 2.5h of tube furnace, adopt argon gas to do shielding gas, to eliminate the stress of aluminium flake inside;
(2) aluminium flake after the anneal is put in the acetone soln, carries out ultrasonic cleaning 15min, at last aluminium flake is carried out electropolishing and handle 5min, clean and remove the polishing fluid on aluminium flake surface, dry in order to anodic oxidation used then to remove the grease on the aluminium flake;
(3) aluminium flake and copper electrode are fixed on the anode of electrolyzer, adding 400ml concentration then in electrolyzer is the oxalic acid electrolytic solution of 0.3mol/L.The copper electrode that aluminium flake is housed is linked to each other with the positive pole of direct supply, and graphite rod links to each other with the negative pole of direct supply, and oxidation voltage is 45V for the first time, and temperature is controlled at 5 ℃, and oxidization time is 6h;
(4) rinse well with the alumina formwork that obtains after the deionized water oxidation for the first time, then alumina formwork is put into mixed acid solution (concentration is respectively the phosphoric acid of 70g/L and the chromic acid of 35g/L mixed in 1: 1 by volume), removed the pellumina that oxidation obtains through the first time.Carry out the oxidation second time then, concrete operations are as follows: adopting 400ml concentration is the oxalic acid solution of 0.3mol/L, and oxidation voltage is 45V for the second time, and temperature is controlled at 5 ℃, and oxidization time is 60～360s for the second time;
(5) utilize anti-plate printing ink to hide the subregion of aluminum oxide film upper surface, draw the part pattern, dry the back aluminum oxide film is continued oxidation 10s;
(6) repeating step (5) is until finishing whole pattern;
(7) utilize the acetone ultrasonic cleaning to remove anti-plate printing ink;
(8) utilize saturated CuCl
2Peel off the aluminium base of the pellumina back side, thereby obtain having the ultrathin alumina film of forming pattern by different colours.
Claims (6)
1. a color tunable and have the preparation method of the aluminum oxide film of high saturation is characterized in that may further comprise the steps:
(1) be that high-purity aluminium flake of 99.999% places under 500 ℃ in the tube furnace with purity, adopt argon gas to do shielding gas, anneal 2.5h eliminates the stress of aluminium flake inside;
(2) aluminium flake after the anneal is put in the acetone soln, carries out ultrasonic cleaning 15min, remove the grease on the aluminium flake, at last aluminium flake is carried out electropolishing and handle 5min, clean and remove the polishing fluid on aluminium flake surface, dry in order to anodic oxidation used then;
(3) aluminium flake and copper electrode are fixed on the anode of electrolyzer, adding concentration then in electrolyzer is the oxalic acid electrolytic solution of 0.3mol/L, the copper electrode that aluminium flake is housed is linked to each other with the positive pole of direct supply, graphite rod links to each other with the negative pole of direct supply, be separately fixed at the electrolyzer two ends, carry out the oxidation first time, anodic oxidation voltage is 45V for the first time, temperature is controlled at 5 ℃, and oxidization time is 6h;
(4) rinse well with the alumina formwork that obtains after the deionized water oxidation for the first time, then alumina formwork is put into and be respectively the mixed acid solution that the chromic acid of the phosphoric acid of 70g/L and 35g/L mixed in 1: 1 by volume by concentration and remove the pellumina that oxidation obtains through the first time, carry out the oxidation second time then, concrete operations are as follows: adding concentration in the electrolyzer is the oxalic acid solution of 0.3mol/L, oxidation voltage is 45V for the second time, temperature is controlled at 5 ℃, and oxidization time is 100～160s for the second time;
(5) after anodic oxidation is for the second time finished, remove the aluminium base of the pellumina back side, obtain the aluminum oxide film of the different colours formed by porous layer and blocking layer with saturated Cupric Chloride Solution.
2. preparation method according to claim 1 is characterized in that oxidization time 100s for the second time.
3. preparation method according to claim 1 is characterized in that oxidization time 110s for the second time.
4. preparation method according to claim 1 is characterized in that oxidization time 120s for the second time.
5. preparation method according to claim 1 is characterized in that oxidization time 140s for the second time.
6. preparation method according to claim 1 is characterized in that oxidization time 160s for the second time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422136A (en) * | 2013-08-30 | 2013-12-04 | 河北民族师范学院 | Aluminum oxide thin film of porous structure with different pore depths and different pore diameters and preparation method of aluminum oxide thin film |
| CN107268053A (en) * | 2016-04-06 | 2017-10-20 | 林明达 | The method and its structure that pattern is generated on oxide-film are electroplated in metal surface |
| CN109989086A (en) * | 2019-04-19 | 2019-07-09 | 河北工业大学 | A kind of preparation method of the porous aluminas photon crystal film with high saturation schemochrome |
-
2011
- 2011-04-02 CN CN 201110082333 patent/CN102181901A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 《Journal of Physics: Conference Series》 20110309 Xulongqi Wang et a A study of color modulation of porous alumina processed by physical vapor deposition 3. Theoretical analysis 1-6 第276卷, 第1期 * |
| 《光谱学与光谱分析》 20060331 张冬仙等 多孔氧化铝薄膜的纳米结构和光谱特性研究 第411-414页 全文 第26卷, 第3期 * |
| 《河北师范大学学报（自然科学版）》 20081130 范胜华等 氧化铝模板的制备及表征 实验部分 1-6 第32卷, 第6期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422136A (en) * | 2013-08-30 | 2013-12-04 | 河北民族师范学院 | Aluminum oxide thin film of porous structure with different pore depths and different pore diameters and preparation method of aluminum oxide thin film |
| CN107268053A (en) * | 2016-04-06 | 2017-10-20 | 林明达 | The method and its structure that pattern is generated on oxide-film are electroplated in metal surface |
| CN109989086A (en) * | 2019-04-19 | 2019-07-09 | 河北工业大学 | A kind of preparation method of the porous aluminas photon crystal film with high saturation schemochrome |
| CN109989086B (en) * | 2019-04-19 | 2020-11-03 | 河北工业大学 | Preparation method of porous alumina photonic crystal film with high-saturation structural color |
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Application publication date: 20110914 |