CN1192129C - Alumina template for preparing nano material and preparation method of template - Google Patents
Alumina template for preparing nano material and preparation method of template Download PDFInfo
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- CN1192129C CN1192129C CNB021384703A CN02138470A CN1192129C CN 1192129 C CN1192129 C CN 1192129C CN B021384703 A CNB021384703 A CN B021384703A CN 02138470 A CN02138470 A CN 02138470A CN 1192129 C CN1192129 C CN 1192129C
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000004888 barrier function Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000002070 nanowire Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
An alumina template for preparing nano material and its preparing process features that a template has different regions, all regions have the same density of nano pores, the same region has the same diameter of nano pores, and different regions have different diameters of nano pores. The preparation method is to remove the barrier layer by adopting a multi-step method, namely, areas are divided on the template according to set positions, and the barrier layers in different areas are gradually removed by using phosphoric acid solution. The pore diameter adjustable alumina template provides a convenient way for synthesizing the nano material, and the preparation method is simple and feasible.
Description
The technical field is as follows:
the present invention relates to an alumina template for preparing a nanomaterial and a method for preparing the template.
Background art:
with the continuous development of scientific technology, many new sciences are continuously made. Nanomaterial science is one example. The preparation of the nano material is the basis for the application of the nano material in practice. The methods adopted for preparing the nano materials at present are as follows: templating, vapor deposition, photolithography, liquid phase methods, and the like. And the template method is the most basic method. There are currently about four more mature templates: carbon tubes, ion beam etched carbon films, biological micro-micelles and alumina templates. The alumina template has the characteristics of good mechanical strength, adjustable hole length-diameter ratio (hole length/hole diameter) and the like, so that the alumina template becomes one of the most widely applied templates at present. The nano-pore array system is obtained by putting 99.99 percentpure aluminum sheets in proper acid solution (such as oxalic acid, sulfuric acid, phosphoric acid and the like) and carrying out anodic oxidation. Since the early 90 s, a number of nanostructured materials have been successfully synthesized using templates derived from alumina self-assembly, such as: nano-fiber (nano-fiber), nano-rod (nano-rod), nano-tube (nano-tube), and nano-wire (nano-wire), etc. These nanomaterials show promising application prospects, and some of them have even come out of the laboratory stage, for example, carbon nanotubes have been used for field emission.
However, the alumina template is currently applied to the same piece of alumina template, and the pore diameters of the nano-pores are consistent, which brings difficulty to research on the relationship between the physical properties and the diameters of the nano-materials and is also not beneficial to the realization of devices of the nano-materials. Moreover, research results in recent ten years show that scientists can obtain alumina templates with different nano-pore diameters by adjusting anode oxidation voltage, acid solution concentration, temperature and the like, but according to the existing method, the method for obtaining nano-pores with different pore diameters on the same template is impossible.
The invention content is as follows:
the technical problem to be solved by the invention is to avoid the defects of the prior art, provide a novel alumina template for preparing nano materials and a preparation method of the template, and provide a convenient way for synthesizing the nano materials.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the alumina template of the invention is characterized in that one template has different areas, the density of the nano-pores in all the areas is the same, the pore diameter of the nano-pores in the same area is the same, and the pore diameter of the nano-pores in different areas is different.
The pure aluminum sheet is subjected to anodic oxidation corrosion in an acid solution, and the structure of the pure aluminum sheet comprises three parts from top to bottom, including: the upper layer, the porous alumina membrane layer, the middle layer, the dense alumina barrier layer and the bottom layer, the non-oxidized aluminum layer. When in use, phosphoric acid solution and HgCl are respectively used2The solution removes the intermediate and bottom layers and when the dense alumina barrier layer is removed, the porous alumina of the upper layer will inevitably be reamed. Based on the principle, the template preparation method is characterized in that the barrier layer is removed by adopting a multi-step method, namely, areas are divided on the template according to set positions, the barrier layers in different areas are gradually removed by phosphoric acid solution, and the following operation steps are adopted:
a. placing a pure aluminum sheet in an acid solution, and preparing the pure aluminum sheet into a three-layer structure from top to bottom through anodic oxidation, wherein the three-layer structure comprises an upper layer, a porous alumina membrane layer, a middle layer, a compact alumina barrier layer and a bottom layer, namely an unoxidized aluminum layer;
b. dividing different areas on the sheet with the three-layer structure obtained in the step a, and discharging the serial numbers of the areas from large aperture to small aperture as an area I, an area II to an area n;
c. removing the bottom aluminum layer (6) of the area I, and corroding the dense aluminum oxide barrier layer (5) of the area I by using phosphoric acid solution to thinthe area I;
d. removing the bottom aluminum layer (6) of the area II, and simultaneously corroding the dense alumina barrier layers (5) of the area I and the area II by using phosphoric acid solution to thin the alumina barrier layers (5) of the two areas;
e. and gradually operating according to the method until the bottom aluminum layer of the region n is finally removed, and corroding by using a phosphoric acid solution to completely remove the dense alumina barrier layer in the middle layer of each region.
Compared with the prior art, the invention has the beneficial effects that:
1. optical properties. Both theory and experiment have demonstrated that the optical properties of nanowires (tubes, rods) vary accordingly with diameter. The nano-wire (tube, rod) array with the same density and the same diameter on the same template, which is obtained by assembling the alumina templates with different apertures, can realize the adjustability of the optical property on the same template, thereby laying the foundation for the device formation of the nano-material.
2. Electrical properties. The electrical properties of the nanowires (tubes, rods) are likewise not related to their diameter. It has been found that the electron transport properties of different diameter bismuth nanowires differ and at a certain diameter a transition from semimetal to semiconductor will occur. And if the carbon nano tube has the field emission effect, the adjustability of the field emission effect can be realized on the carbon nano tube arrays with the same density and different diameters of the same template hole.
3. Magnetic properties. The adjustable magnetic property of the nanowire (tube and rod) array of magnetic materials (iron, cobalt, nickel and alloy) with the same density and different diameters on the same template can be realized by assembling the alumina template with adjustable pore diameter.
The preparation method has the beneficial effects that:
the alumina template obtained by adopting the method for removing the barrier layer by multiple steps has the advantages of reliability, simple operation, large aperture change range and the like.
Description of the drawings:
FIG. 1 is a schematic view of a region division structure of an alumina template according to the present invention.
FIG. 2 is a schematic cross-sectional view of the alumina template of the present invention during the preparation thereof.
The specific implementation mode is as follows:
the alumina template in the embodiment has different areas on one template, the density of the nano-pores 7 in all the areas is the same, the pore diameter of the nano-pores 7 in the same area is the same, and the pore diameter of the nano-pores 7 in different areas is different.
Referring to the drawings, the different regions may be a central circle region divided by different radii with the center of the template as a center, and annular regions other than the central circle. The different zones may also be divided in other ways as desired.
Fig. 1 shows that the regions in this embodiment are a central circular region 1, an inner ring region 2 and an outer ring region 3, which are divided by taking the center of the template as the center and using different radii, wherein the density of the nanopores in each region is the same, the pore diameters of the nanopores in the same region are the same, and the pore diameters of the nanopores in different regions are different. The nanopore aperture in the central circular region 1 is largest, followed by the inner annular region 2, and the nanopore aperture is smallest, followed by the outer annular region 3.
For the alumina template in the embodiment, the preparation method thereof adopts the following operation steps:
1. the pure aluminum flake is placed in an acidic solution, which may be oxalic acid: 0.3M, 12 ℃ and 40V. Acid solution or sulfuric acid: 0.3M, 0 ℃ and 27 volts. After anodic oxidation for 8 hours, the anode material is made into a three-layer structure as shown in figure 2 from top to bottom, namely an upper layer, a porous alumina membrane layer 4, a middle layer, a compact alumina barrier layer 5 and a bottom layer, an unoxidized aluminum layer 6.
2. And (3) dividing different areas on the sheet with the three-layer structure obtained in the step (1), and taking the serial numbers of the discharge areas from large to small in aperture as a central circle area (1), an inner ring area (2) and an outer ring area (3).
3. Removing the bottom aluminum layer 6 of the central circular area 1, and corroding the central circular area for 10 minutes at room temperature by using 5 wt% phosphoric acid solution, wherein the dense alumina barrier layer 5 of the area is thinned by the process;
4. the bottom aluminum layer 6 of the inner annular region 2 is removed and etched with a 5 wt% phosphoric acid solution at room temperature for 10 minutes, which further thins the dense alumina barrier layer of the central circular region 1 and at the same time thins the dense alumina barrier layer of the inner annular region 2.
5. The bottom aluminum layer 6 of the outer ring region 3 was finally removed and etched with a 5 wt% phosphoric acid solution at room temperature for 30 minutes, by which process the dense alumina barrier layer 5 of each region was completely removed and at the same time the nanopores in the central circular region 1 and the inner ring region 2 were more or less reamed.
In the above process, the aluminum layer is removed by using saturated HgCl2Solution of aluminum with HgCl according to the principle of chemical displacement reaction2The solution will react as follows: the mercury formed by the reaction can be washed away with deionized water. When removing the aluminum layer in a certain area, other positions need to be protected in a conventional manner.
Experiments show that:
after the steps of the alumina template obtained from oxalic acid under corresponding conditions are completed, the pore diameters of the central circle region 1, the inner ring region 2 and the outer ring region 3 are 110nm, 80nm and 40nm in sequence, and the pore densities of all the regions are consistent.
Different conditions may result in different degrees of reaming. After the alumina template obtained in the sulfuric acid under the corresponding conditions is subjected to the steps, the pore diameters in the central circle region 1, the inner ring region 2 and the outer ring region 3 are 60nm, 40nm and 20nm in sequence, and the pore densities of all the regions are consistent.
Direct observation with a scanning microscope can confirm the feasibility of the method.
Claims (3)
1. An alumina template for preparing nano-materials is characterized in that different areas (1, 2, 3) are arranged on one template, the density of nano-holes (7) in all the areas is the same, the pore diameter of the nano-holes (7) in the same area is the same, and the pore diameter of the nano-holes (7) in different areas is different.
2. The alumina template for nanomaterial fabrication according to claim 1, wherein the different regions are a central circle region (1) divided by different radii with the center of the template as a center, and annular ring regions (2, 3) other than the central circle.
3. A method for preparing an alumina template for nanomaterial preparation according to claim 1, characterized by comprising the following steps:
a. placing a pure aluminum sheet in an acid solution, and preparing the pure aluminum sheet into a three-layer structure from top to bottom through anodic oxidation, namely an upper layer, namely a porous alumina membrane layer (4), a middle layer, namely a compact alumina barrier layer (5), and a bottom layer, namely an unoxidized aluminum layer (6);
b. dividing different areas on the sheet with the three-layer structure obtained in the step a, and discharging the serial numbers of the areas from large aperture to small aperture as an area I, an area II to an area n;
c. removing the bottom aluminum layer (6) of the area I, and corroding the dense aluminum oxide barrier layer (5) of the area I by using phosphoric acid solution to thin the area I;
d. removing the bottom aluminum layer (6) of the area II, and simultaneously corroding the dense alumina barrier layers (5) of the area I and the area II by using phosphoric acid solution to thin the alumina barrier layers (5) of the two areas;
e. the operation is carried out step by step according to the method until the bottom aluminum layer (6) of the area n is finally removed, and the middle layer dense alumina barrier layer (5) of each area is completely removed by phosphoric acid solution corrosion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021384703A CN1192129C (en) | 2002-10-18 | 2002-10-18 | Alumina template for preparing nano material and preparation method of template |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021384703A CN1192129C (en) | 2002-10-18 | 2002-10-18 | Alumina template for preparing nano material and preparation method of template |
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| CN1490244A CN1490244A (en) | 2004-04-21 |
| CN1192129C true CN1192129C (en) | 2005-03-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100528941C (en) * | 2004-07-02 | 2009-08-19 | 中国科学院上海应用物理研究所 | Process for preparing medical high molecular super hydrophobic film |
| CN100441348C (en) * | 2006-05-12 | 2008-12-10 | 天津大学 | Metal nano nickel tube and preparation method thereof |
| 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 |
| CN104975320B (en) * | 2014-04-13 | 2018-02-23 | 山东建筑大学 | Prepare cylinder shape alumina formwork of nano material and preparation method thereof |
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