CN103422136B - A kind of have aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof - Google Patents
A kind of have aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof Download PDFInfo
- Publication number
- CN103422136B CN103422136B CN201310389049.6A CN201310389049A CN103422136B CN 103422136 B CN103422136 B CN 103422136B CN 201310389049 A CN201310389049 A CN 201310389049A CN 103422136 B CN103422136 B CN 103422136B
- Authority
- CN
- China
- Prior art keywords
- hole
- district
- oxide film
- aluminum oxide
- hole district
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses and a kind of there is aluminum oxide film of the multiple hole structure in different hole depth and aperture and preparation method thereof.The surface arrangement of this aluminum oxide film is by the first hole district be made up of multiple hole and the second hole district, the average hole depth in described first hole district is greater than the average hole depth in the second hole district, and the mean pore size in described first hole district is greater than the mean pore size in the second hole district.Under specific experimental conditions, described aluminum oxide film can demonstrate the schemochrome of two kinds of different colors, and two kinds of colors and shared region area are than controlled.Carry out electrooxidation pretreated aluminium foil is improved the planeness on surface by pre-electrooxidation after just can obtain, this aluminum oxide film only can need be prepared by once oxidation technique, simplifies preparation flow, reduces preparation cost.
Description
Technical field
The present invention relates to the technical field of aluminum oxide film, particularly relate to and a kind of there is aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof.
Background technology
Because the aluminum oxide film with nano aperture is broad-band gap metal oxide semiconductor material, there is thermostability, erosion resistance, chemical stability and high-k, be widely used in the synthesis of ordered nano-structure.Along with going deep into of photonic crystal research, the schemochrome problem about aluminum oxide film there has also been certain research.1969, the people such as Diggle were reported in visible-range, had the aluminum oxide film of aluminium base support when thickness is less than 1 μm because interference of light effect can produce bright color.2007, people's reports such as northeastern Japan university Wang utilized CVD technology on aluminum oxide film after deposition of carbon nanotubes, have prepared the aluminum oxide film that color saturation is higher.Subsequently, 2010, solid institute of Hefei material science research institute of Chinese Academy of Sciences doctor Zhao Xianglong achieved impressive progress in the study on regulation of carbon pipe composite alumina laminated film color, achieved the finely regulating to carbon pipe composite alumina laminated film color.2011, Hebei Normal University Sun Huiyuan taught the alumina composite film that group adopts repeatedly oxidation style to prepare to have change colour bar feature.
But up to the present also do not adopt preparation technology on same aluminium foil, prepare the report of different hole depth and aperture aluminum oxide film.And, the existing preparation with the aluminum oxide film of various structures look is taked repeatedly to be oxidized mostly, this sample preparation method is loaded down with trivial details, preparation cost is higher, and the present invention only adopts a preparation process, two kinds of schemochromes can be obtained on same aluminium foil under specific experimental conditions, greatly reduce experimental cost, simplify experimentation.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of vesicular structure aluminum oxide film with different hole depth and aperture, and this aluminum oxide film can be obtained by once oxidation, and preparation is simple, and cost is lower.
A kind of aluminum oxide film with multiple hole structure, the surface arrangement of aluminum oxide film is by the first hole district be made up of multiple hole and the second hole district, the average hole depth in described first hole district is greater than the average hole depth in the second hole district, and the mean pore size in described first hole district is greater than the mean pore size in the second hole district.
Wherein, the average hole depth in described first hole district and the second hole district is between 100nm ~ 240um.
Wherein, the area ratio in described first hole district and the second hole district is 13 ~ 1.2, and described first hole district is 1.5 ~ 1.7 with the ratio of the mean pore size in the second hole district.
Wherein, the surface arrangement of aluminum oxide film is connected the transition hole district in described first hole district and the second hole district respectively by the two ends be made up of multiple hole, the hole depth of the hole in described transition hole district is successively decreased from the described first hole district part of connection to connection second hole district part, successively decreases from the described first hole district part of connection to connection second hole district part in the aperture of the hole in described transition hole district.
Wherein, described aluminum oxide film is the film that can produce two kinds of schemochromes.
More than have in the technical scheme of vesicular structure aluminum oxide film in different hole depth and aperture, hole is dot matrix arrangement.The average hole depth in hole district refers to pertusate mean value in certain hole district, can be arithmetical av.In like manner, mean pore size refers to pertusate mean value in certain hole district.Because the hole depth with the hole in a hole district is substantially identical with aperture, for simplicity, the hole depth of holes all for same hole district and aperture are considered as identical by the present invention.
The present invention provides a kind of preparation method with the vesicular structure aluminum oxide film in different hole depth and aperture on the other hand, and the method adopts once oxidation method, and make preparation simple, cost is lower.
A preparation method for aluminum oxide film described above, comprises the following steps:
(1) pre-treatment is carried out to aluminium foil;
(2) become inclination angle to insert in electrolytic solution as anode and with negative electrode on aluminium foil after pretreatment and carry out pre-electrooxidation;
(3) become as anode and with negative electrode by the aluminium foil through pre-electrooxidation inclination angle to insert described electrolytic solution and carry out electrooxidation.
Wherein, described inclination angle is 15 ~ 60 °, and described electrolytic solution is the oxalic acid of 0.285 ~ 0.315mol/L.
Wherein, the voltage of described pre-electrooxidation and electrooxidation is 40 ~ 50V, and the time of described pre-electrooxidation is 4 ~ 6h, and the time of described electrooxidation is 30s ~ 12h.
Wherein, the voltage of described electrooxidation is 40 ~ 50V, when the time of electrooxidation is 30s ~ 200s, same aluminium foil obtains the aluminum oxide film with two kinds of schemochromes simultaneously.
Wherein, between step (2) and step (3), comprise the step of deoxidation film, be specially: the aluminium foil after pre-electrooxidation is inserted in mineral acid mixing solutions and soak 8 ~ 12h; Described pre-treatment comprises successively according to order from front to back cuts out, cleans, anneals and electrochemical etching.
Wherein, described electrolyte level is in electrolyzer, and described anode is 1.4 ~ 1.8cm to the distance L of the sidewall of described electrolyzer, and described anodes centre is 1.6 ~ 2.0cm to the vertical range H of the bottom of described electrolyzer.
What deserves to be explained is, in step (3), oxidation voltage is 40 ~ 50V, and the angle between negative electrode and positive electrode is 15 ° ~ 60 °, and oxidization time is between 30 ~ 200s, can obtain the aluminum oxide film with two kinds of schemochromes on same aluminium foil, shared by often kind of schemochrome, region area is than controlled.
In the technical scheme of above preparation method, the object of pre-electrooxidation is the planeness in order to improve aluminium foil further.In the process of pre-electrooxidation, in tens seconds after energising, electric current falls sharply as several milliamperes from hundreds of milliampere rapidly, then be elevated to a stationary value gradually, the reason of this kind of change of electric current is explained as follows: high-purity aluminum foil, under the effect of extra electric field, electrochemical reaction occurs, and generates one deck aluminum oxide film, cause strength of electric field to decline, electric current declines rapidly.Along with the carrying out of oxidising process, forming the place of film, aluminum oxide starts to dissolve gradually, forms path, makes ion can movement mutually, and electric current increases gradually.When the formation of oxide compound and dissolving reach running balance, electric current tends towards stability, and porous layer constantly thickens, and finally forms porous anodic alumina film.
The surface arrangement of aluminum oxide film of the present invention is by the first hole district be made up of multiple hole and the second hole district, the average hole depth in described first hole district is greater than the average hole depth in the second hole district, and the mean pore size in described first hole district is greater than the mean pore size in the second hole district.Carry out electrooxidation pretreated aluminium foil is improved the planeness on surface by pre-electrooxidation after just can obtain, this aluminum oxide film only can need be prepared by once oxidation technique, simplifies preparation flow, reduces preparation cost.
Accompanying drawing explanation
Fig. 1 of the present inventionly prepares aluminum oxide film film device schematic diagram;
Fig. 2 of the present inventionly prepares aluminum oxide film electrochemical reaction power line schematic diagram;
Fig. 3 is the surperficial SEM figure of the aluminum oxide film of the embodiment of the present invention 1;
Fig. 4 is surface and the section S EM figure of the aluminum oxide film of the embodiment of the present invention 2;
Fig. 5 is hole depth and cross section, the aperture fitted figure of the aluminum oxide film of the embodiment of the present invention 1 ~ 10;
Fig. 6 is the embodiment of the present invention 3,4,2,5 aluminum oxide film digital photograph figure;
Fig. 7 is the embodiment of the present invention 6 ~ 10 aluminum oxide film digital photograph figure;
Fig. 8 is the aluminum oxide film reflected light spectrogram of the embodiment of the present invention 2.
In figure:
1-electrolyzer; 2-electrolytic solution; 3-carbon-point; 4-aluminium foil; 41-aluminium lamination; 42-alumina layer; 43-hole; 5-copper conductor.
Embodiment
Below respectively in conjunction with the embodiments and accompanying drawing the present invention is described in further detail.
The unit type adopted in following examples and Cheng Chan producer as follows: Ultrasonic Cleaners (model PS-08A, Shenzhen constant force ultrasonic equipment company limited); Quartz tube furnace (model HTL1100-60, Hefei Ke Jing Materials Technology Ltd.); Direct supply (model is DC-1760, Hefei Da Chun Electronics Co., Ltd.); Digital camera (model is EOS600D, Canon (China) Co., Ltd); Scanning electron microscope (model is S-4800, Japanese Hitachi company); Ultraviolet-visible pectrophotometer (model is Hitachi U-3010, HIT).
Embodiment 1
Aluminum oxide film is prepared according to following steps:
(1) be 99.999% purity, thickness is the disk that the high-purity aluminum foil of 0.3mm is cut into about 2cm, ultrasonic cleaning is placed in acetone soln 30 minutes after pressing, put into alcohol ultrasonic cleaning subsequently 30 minutes, finally repeatedly rinse in deionized water, be placed on after drying in quartz tube furnace, at 400 DEG C of vacuum annealing 2h, be cooled to room temperature.Then carry out electropolishing process to the high-purity aluminum foil after annealing, electropolishing liquid is the HCLO of volume ratio 1:4
4with the mixed solution of dehydrated alcohol, using aluminium foil as anode, carbon-point, as negative electrode, carries out electrooxidation 50s at voltage about 20V, repeatedly rinses post-drying.
(2) high-purity aluminum foil after polishing is positioned in electrolyzer as anode, the carbon-point being 0.6mm with long 8cm, diameter is for negative electrode, anode and negative electrode are inserted 0.3mol/L oxalic acid solution, and regulate the angle of anode and negative electrode to be 45 °, as shown in figure (2), then under the voltage of 45V, carry out pre-electrooxidation, after electrooxidation 4h, taking-up cleans up, and the mixing solutions of the phosphoric acid and chromic acid that put it into volume ratio 1:4 soaks 8h, removes oxide film.
(3) aluminium foil removing oxide film is inserted in 0.3mol/L oxalic acid solution, carry out electrooxidation 8h under voltage is 45V condition after, just obtain the aluminum oxide film with the vesicular structure in different hole depth and aperture.
Embodiment 2
Except oxidization time in step (3) is 50s, other conditions are identical with enforcement 1.
Embodiment 3
Except the inclination angle of step (2) Anodic and negative electrode is 15 °, other conditions are identical with enforcement 2.
Embodiment 4
Except the inclination angle of step (2) Anodic and negative electrode is 30 °, other conditions are identical with enforcement 2.
Embodiment 5
Except the inclination angle of step (2) Anodic and negative electrode is 60 °, other conditions are identical with enforcement 2.
Embodiment 6
Except oxidization time in step (3) is 43s, other conditions are identical with enforcement 2.
Embodiment 7
Except oxidization time in step (3) is 47s, other conditions are identical with enforcement 2.
Embodiment 8
Except oxidization time in step (3) is 54s, other conditions are identical with enforcement 2.
Embodiment 9
Except oxidization time in step (3) is 58s, other conditions are identical with enforcement 2.
Embodiment 10
Except oxidization time in step (3) is 61s, other conditions are identical with enforcement 2.
The aluminum oxide film adopting digital camera obtained to embodiment 2 ~ 10 is taken pictures; Scanning electron microscope is adopted to characterize the surface of the aluminum oxide film that embodiment 1 and embodiment 2 obtain and Cross Section Morphology; The reflection spectrum of ultraviolet-visible pectrophotometer to the aluminum oxide film that embodiment 2 obtains is adopted to test.
As shown in Figure 1, be the preparation facilities figure of the aluminum oxide film of the embodiment of the present invention 1 ~ 10.This device comprises electrolyzer 1, anode, negative electrode, copper conductor 5 and power supply that electrolytic solution 2 is housed, aluminium foil 4 is anode, it is connected with positive source by copper conductor 5, aluminium foil 4 is arranged on a sidewall of electrolyzer, aluminium foil distance cell sidewall 1.6cm, aluminium foil width between centers bottom of electrolytic tank vertical range 1.8cm.Negative electrode is carbon-point 3, and negative electrode connects current meter one end by copper conductor 5, and the other end of current meter is connected with power cathode.Carbon-point 3 pitch angle certain with 4 one-tenth, aluminium foil is immersed in electrolytic solution.
As shown in Figure 2, be the electrochemical reaction power line schematic diagram in the preparation process of the aluminum oxide film of the embodiment of the present invention 1 ~ 10.As can be seen from Figure, along with the increase gradually at inclination angle, the area ab section (corresponding second hole district) that aluminium foil is blocked increases gradually.
As shown in Figure 3, for the SEM of the surface topography of the aluminum oxide film of the embodiment of the present invention 1 schemes.In figure, the left side one width is ab section (corresponding second hole district) film surface, and another width is bc section (corresponding first hole district) film surface; As can be seen from scheming us, because ab section is blocked, so cause the voltage being added in ab section alumina barrier layer both sides less, the aperture of its correspondence is less.The corresponding mean pore size of ab section is the corresponding mean pore size of 45nm, bc section is 67nm.
As shown in Figure 4, be aluminum oxide film surface and the section S EM figure of the embodiment of the present invention 2.Aluminum oxide film is made up of aluminium lamination 41, the alumina layer 42 being positioned at aluminium lamination skin 41 and the hole 43 that is positioned at alumina layer.In figure, first row is respectively ab section film surface and cross section from top to bottom from left to right, and mean pore size is 12nm, average film thickness 232nm; The corresponding bc section film surface of secondary series and cross section, mean pore size is 19nm, average film thickness 270nm.Aperture and hole depth determine the schemochrome of different zones.
As shown in Figure 5, be aluminum oxide film hole depth and cross section, the aperture fitted figure of the embodiment of the present invention 1 ~ 10.Because ab section is blocked, so cause the voltage being added in ab section aluminum oxide film both sides less, in identical oxidization time, its corresponding hole depth is more shallow, and aperture is less, and bc section is not blocked, and its corresponding hole depth is comparatively dark, and aperture is larger.
As shown in Figure 6, be the aluminum oxide film digital photograph figure of the embodiment of the present invention 2 ~ 5.Embodiment 3,4,2,5 is followed successively by from left to right in figure.This figure illustrates, along with the increase gradually of negative electrode and positive electrode angle, the area ratio of two kinds of regions of different colours reduces thereupon.
As shown in Figure 7, be the aluminum oxide film digital photograph figure of the embodiment of the present invention 6 ~ 10.In figure, be followed successively by embodiment 6,7,8,9,10 from left to right.Along with the increase of oxidization time, film thickness increases.Because ab section rate of oxidation is less than bc section, so ab section colour-change is comparatively slow, be green by red-purple alternation, bc section colour-change is very fast, is red by purple alternation.
As shown in Figure 8, be the aluminum oxide film reflected light spectrogram of the embodiment of the present invention 2.Reflection peak 448nm and 570nm in reflection spectrum be corresponding purple light and green glow respectively, and its result is identical with the color on digital photograph.
Above embodiment has the aperture of the aluminum oxide film in different hole depth and aperture at nano-scale, it is a kind of good carrier, the catalyzer of many type reaction will be can be applicable in the hole of some these aluminum oxide films of nanomaterial loadings, alkaline earth, rare-earth oxide are carried on carrier by some such as to prepare carbon nanotube used catalyst at present, but the report that also not occur with the aluminum oxide film in different hole depth and aperture be carrier.Perhaps, the aluminum oxide film with the vesicular structure in different hole depth and aperture of the present invention can provide a direction that can explore for the investigator of this area to the novel carbon nano-tube catalyst of preparation.In addition, aluminum oxide film with two kinds of schemochromes prepared by embodiments of the invention presents huge application prospect in false proof, drawing, decoration, makeup, imaging technique, dye sensitization and solar cell, and also significant in the application of other frontiers to opening up aluminum oxide film.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (8)
1. one kind has the aluminum oxide film of the multiple hole structure in different hole depth and aperture, it is characterized in that, the surface arrangement of described aluminum oxide film is by the first hole district be made up of multiple hole and the second hole district, the average hole depth in described first hole district is greater than the average hole depth in the second hole district, and the mean pore size in described first hole district is greater than the mean pore size in the second hole district; The surface arrangement of aluminum oxide film is connected the transition hole district in described first hole district and the second hole district respectively by the two ends be made up of multiple hole, the hole depth of the hole in described transition hole district is successively decreased from the described first hole district part of connection to connection second hole district part, successively decreases from the described first hole district part of connection to connection second hole district part in the aperture of the hole in described transition hole district; The hole depth of the hole in described first hole district is substantially identical with aperture, and the hole depth of the hole in described second hole district is substantially identical with aperture.
2. aluminum oxide film according to claim 1, is characterized in that, the average hole depth in described first hole district and the second hole district is between 100nm ~ 240 μm.
3. aluminum oxide film according to claim 1, is characterized in that, the area ratio in described first hole district and the second hole district is 13 ~ 1.2, and described first hole district is 1.5 ~ 1.7 with the ratio of the mean pore size in the second hole district.
4. a preparation method for aluminum oxide film as claimed in claim 1, is characterized in that, comprises the following steps:
(1) pre-treatment is carried out to aluminium foil;
(2) become inclination angle to insert in electrolytic solution as anode and with negative electrode on aluminium foil after pretreatment and carry out pre-electrooxidation;
(3) become as anode and with negative electrode by the aluminium foil through pre-electrooxidation inclination angle to insert described electrolytic solution and carry out electrooxidation;
Described step (2) becomes inclination angle to place with aluminium foil in step (3) with negative electrode, described inclination angle is 15 ~ 60 °, described anode is 1.4 ~ 1.8cm to the distance L of the sidewall of described electrolyzer, described anodes centre is 1.6 ~ 2.0cm to the vertical range H of the bottom of described electrolyzer, the voltage of described electrooxidation is 40 ~ 50V, until aluminium foil surface formed by the power line originating in this aluminium foil surface be equipped with the electrolyzer interval of electrolytic solution the blocked area that formed and unshielding district.
5. method according to claim 4, is characterized in that, described electrolytic solution is 0.285 ~ 0.315mol/L oxalic acid.
6. method according to claim 4, is characterized in that, the voltage of described pre-electrooxidation is 40 ~ 50V, and the time of described pre-electrooxidation is 4 ~ 6h, and the time of described electrooxidation is 30s ~ 12h.
7. method according to claim 4, is characterized in that, when the time of electrooxidation is 30s ~ 200s, same aluminium foil obtains the aluminum oxide film with two kinds of schemochromes simultaneously.
8. method according to claim 4, is characterized in that, comprises the step of deoxidation film, be specially between step (2) and step (3): inserted by the aluminium foil after pre-electrooxidation in mineral acid mixing solutions and soak 8 ~ 12h; Described pre-treatment comprises successively according to order from front to back cuts out, cleans, anneals and electrochemical etching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310389049.6A CN103422136B (en) | 2013-08-30 | 2013-08-30 | A kind of have aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310389049.6A CN103422136B (en) | 2013-08-30 | 2013-08-30 | A kind of have aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103422136A CN103422136A (en) | 2013-12-04 |
| CN103422136B true CN103422136B (en) | 2016-04-06 |
Family
ID=49647510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310389049.6A Expired - Fee Related CN103422136B (en) | 2013-08-30 | 2013-08-30 | A kind of have aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103422136B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739855B (en) * | 2018-09-19 | 2023-10-03 | 日本轻金属株式会社 | Aluminum member and method for producing same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4834891B2 (en) * | 2006-08-11 | 2011-12-14 | 山梨県 | Surface processing method of metal material and metal substrate using this processing method |
| CN101104944A (en) * | 2007-04-19 | 2008-01-16 | 上海交通大学 | Process for preparing ordered porous aluminum oxide thin film |
| CN101838834B (en) * | 2010-05-21 | 2012-01-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Modulation method for shape morphing of hole of anodic aluminum oxide template |
| CN102181901A (en) * | 2011-04-02 | 2011-09-14 | 河北师范大学 | Method for preparing alumina membrane with adjustable color and high saturation |
| CN102925947B (en) * | 2011-08-09 | 2015-07-08 | 中国科学院化学研究所 | Preparation method for anode alumina template having gradient nanometer pore size |
| CN103060878B (en) * | 2013-01-31 | 2016-01-20 | 中国科学院合肥物质科学研究院 | Erect silver nanometer column array in porous alumina formwork aperture and its production and use |
-
2013
- 2013-08-30 CN CN201310389049.6A patent/CN103422136B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103422136A (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103436936B (en) | A kind of have aluminum oxide film of the porous of gradual change hole depth and preparation method thereof | |
| CN101294298B (en) | Electrochemical polishing method for high purity aluminum under ultrasonic agitation | |
| CN107502936A (en) | A kind of method for obtaining large aperture doubled via AAO films | |
| CN103147108B (en) | A kind of anodic alumina films and preparation method thereof | |
| CN101499417B (en) | Method for implementing image transfer on semiconductor material by anodised aluminum template | |
| CN105734606A (en) | Structure of ultrathin membrane electrode for SPE water electrolysis and preparation and application of structure | |
| Xing et al. | Influence of substrate morphology on the growth and properties of TiO2 nanotubes in HBF4-based electrolyte | |
| CN103014755A (en) | Fabrication method of long-life titanium base electrode | |
| CN106011969B (en) | Ni-based upper gold nano grain array and preparation method thereof | |
| CN103451703A (en) | Alumina film with iridescent structural color and preparation method thereof | |
| CN104805475A (en) | Magnetic Co nanowire/porous alumina composite film, preparation method and application of magnetic Co nanowire/porous alumina composite film | |
| CN104562097B (en) | A kind of preparation method of self-supporting nickel nano tube/linear array film | |
| CN103014800B (en) | The preparation method of the graphite-based plumbic oxide catalysis electrode of cerium dopping | |
| CN103422136B (en) | A kind of have aluminum oxide film of the vesicular structure in different hole depth and aperture and preparation method thereof | |
| CN104805473A (en) | Co nanowire/porous alumina composite film as well as preparation method and application thereof | |
| Sankar et al. | Synthesis and characterization of cadmium selenide nanostructures on porous aluminum oxide templates by high frequency alternating current electrolysis | |
| CN104805474B (en) | Annular carbon electrode and the method for preparing Co nano wires/aluminum oxide film using it | |
| CN102017262B (en) | Inorganic ion conductive membrane, fuel cell containing the same and manufacturing method thereof | |
| TWI627316B (en) | A method for making a tubular anodic aluminum oxide with nanometer or sub-micron pores | |
| CN112952052A (en) | Zinc/carbon nanotube foam composite material and preparation method and application thereof | |
| Lin et al. | Templated fabrication of nanostructured Ni brush for hydrogen evolution reaction | |
| CN106801242B (en) | The quickly method of the preparation big pitch of holes porous anodic alumina films of large area high-sequential | |
| JP2007026839A (en) | Electrolyte membrane for fuel cell and manufacturing method for electrolyte membrane for fuel cell | |
| CN106917126B (en) | Porous alumina film, Co nanowire/alumina composite film and preparation method thereof | |
| EP4095287A1 (en) | Porous electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160406 Termination date: 20180830 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |