CN104975323B - Prepare sine surface shape alumina formwork of nano material and preparation method thereof - Google Patents
Prepare sine surface shape alumina formwork of nano material and preparation method thereof Download PDFInfo
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- CN104975323B CN104975323B CN201410152802.4A CN201410152802A CN104975323B CN 104975323 B CN104975323 B CN 104975323B CN 201410152802 A CN201410152802 A CN 201410152802A CN 104975323 B CN104975323 B CN 104975323B
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Abstract
A kind of sine surface shape alumina formwork for preparing nano material and preparation method thereof.It is characterized in that the inside and outside two sides of template is sine surface, conical nano aperture array is along the radial ordered arrangement of sine surface vertical direction, the pore size and varying aperture rate of conical nano-pore can also be adjusted along the tangential gradual change of sinusoidal line by changing cycle, amplitude and the anodizing time of sine surface.Its preparation method is to obtain the high-purity aluminium flake of sine surface shape after polishing, anodic oxidation, removal barrier layer.Synthesis of the sine surface shape alumina formwork to nano material in the present invention provides a kind of convenient way, its preparation method simple possible.
Description
Technical field：
The present invention relates to for preparing the sine surface shape alumina formwork of nano material and the preparation method of the template.
Background technology：
With the continuous development of scientific technology, many new subjects constantly rise.Nanomaterial science is wherein one.Receive
The preparation of rice material is the basis of Application of micron.Preparing the method that nano material uses more at present has：Template, gas phase are sunk
Area method, photoetching process, liquid phase method, ibl etc..And template therein is a kind of most basic method.At present compared with into
About four kinds of ripe template：CNT, ion beam etching carbon film, the micro- micella of biology and alumina formwork.Alumina formwork
Due to having the characteristics that hole density is big, nano-pore draw ratio (hole length/bore dia) is adjustable, it is the widest to become current application
One of general template.It is that 99.99% fine aluminium piece is placed in appropriate acid solution (such as oxalic acid, sulfuric acid or phosphoric acid),
The nano aperture array system obtained by anodic oxidation.Since the beginning of the nineties in last century, people utilize alumina formwork
Many nano structural materials are successfully synthesized, such as：Nanofiber, nanometer rods, nanotube and nano wire etc..These nano material exhibitions
Reveal the application prospect for making us admiring, some have even walked out laboratory stage, as CNT is used for Flied emission, semiconductor
Nanowire lasers etc..
But on alumina formwork, what is be applied at present is planar shaped alumina formwork, i.e. its two tables up and down
Face is all plane, is unfavorable for the device that nano material realizes function.Moreover, the nano-pore in planar shaped alumina formwork
Straight-tube shape and arranged in parallel is presented in hole, and the function using the nano material of this template assemblies is single.According to existing method,
Realize that the alumina formwork of the radial ordered arrangement of conical nano aperture is impossible.
The content of the invention：
The present invention is in order to solve the deficiencies in the prior art, there is provided a kind of sine surface shape oxidation aluminum dipping form for preparing nano material
Plate and preparation method thereof.A kind of convenient way is provided for the synthesis of nano material.
The technical proposal for solving the technical problem of the invention is：
The characteristics of sine surface shape alumina formwork of the present invention is that the inside and outside two sides of template is sine surface, and cone is received
Metre hole hole is along the radial ordered arrangement of sine surface vertical direction, and conical nano-pore pore size and rate of change edge are sinusoidal
The tangential gradual change of line, and can also be adjusted by changing anodizing time.Sine surface shape aluminium flake is by polishing, anodic oxygen
Change, obtain sine surface shape alumina formwork after removal barrier layer.
The specific preparation method of the present invention is included following steps in sequence：
1. the high-purity aluminium flake of planar shaped is covered in into sine surface die surface, sine surface shape is obtained after forging pressing and shaping
Aluminium flake, or remove sine surface mould again after sine surface die surface vacuum evaporated aluminium and obtain sine surface shape aluminium flake；
2. sine surface shape aluminium flake polishes 4-5 minutes in the mixed liquor of ethanol and perchloric acid；
3. take out aluminium flake deionized water rinsing 3-5 times；
4. sine surface shape aluminium flake is put into oxalic acid solution Anodic Oxidation 20 hours；
5. remove the oxide layer on sine surface shape aluminium flake；
6. sine surface shape aluminium flake carries out second of anodic oxidation 8 hours in oxalic acid solution；
7. remove unoxidized aluminium lamination and barrier layer,
8. with deionized water rinsing 3-5 times, dry at room temperature.
Compared with the prior art, the present invention has following technique effect：
1st, geometrical property.The surfaces externally and internally of sine surface shape alumina formwork is all sine surface, relative to plane template
There is greater advantage in terms of the device of nano material, for example, by sine surface shape template can be made sine surface grating,
Fiber waveguide etc..
2nd, electrical properties.Arranged in parallel, uniform diameter nano wire (pipe, rod) and radial ordered arrangement, cone are received
The electrical properties of rice noodles (pipe, rod) have very big difference.It has been found that the Electronic Transport Properties of different-diameter bismuth nano-wire are not
Together, or be semimetal or be semiconductor, using sine surface shape alumina formwork can assemble to obtain radial ordered arrangement and
Nano wire (pipe, rod) array of Diameter Gradual Change, so as to realize transformation of the semimetal to semiconductor on a nano wire, it is
The device of nano material is laid a good foundation.
3rd, optical property.Theoretical and experiment is all it was demonstrated that radial ordered arrangement, the nano wire (pipe, rod) of Diameter Gradual Change
With unusual optical property.For example the silver nano line array of radial arrangement can realize that sub-wavelength super-resolution zooms into picture
Deng.Using sine surface shape alumina formwork can assemble to obtain radial ordered arrangement and Diameter Gradual Change nano wire (pipe,
Rod) array, it is possible to achieve the excellent optical property of nano material.
This preparation method has the beneficial effect that：
The preparation method of sine surface shape alumina formwork is simple to operate, reliable, taper pore size and varying aperture rate
It can be adjusted by changing cycle, amplitude and the anodizing time of sine surface.
Brief description of the drawings：
Figure is pictorial diagram of the sine surface shape aluminium flake of the present invention after anodic oxidation.
Embodiment：
The inside and outside two sides of sine surface shape alumina formwork in the present embodiment is all sine surface, conical nano aperture
Along the radial ordered arrangement of sine surface vertical direction, the pore size and varying aperture rate of conical nano-pore are cut along sinusoidal line
To gradual change, and can also be adjusted by changing cycle, amplitude and the anodizing time of sine surface.Dotted arrow in figure
Represent that template sinusoidal line is tangential.
For the alumina formwork in the present embodiment, its preparation method concretely comprises the following steps：
(1) the high-purity aluminium flake of planar shaped is covered in sine surface die surface, sine surface is obtained after forging pressing and shaping
Shape aluminium flake, or remove sine surface mould again after sine surface die surface vacuum evaporated aluminium and obtain sine surface shape aluminium
Piece；
(2) sine surface shape aluminium flake polishes 4-5 minutes, electricity in the mixed liquor of ethanol and perchloric acid (volume ratio 5: 1)
It is 10 degrees Celsius to press as 14-15 volts, temperature；
(3) aluminium flake deionized water rinsing 3-5 times is taken out；
(4) sine surface shape aluminium flake being put into 0.3M oxalic acid solutions Anodic Oxidation 20 hours, oxidation voltage is 40 volts,
Temperature is 5 degrees Celsius；
(5) by the aluminium flake that (4) obtain be put into by volume 1: 1 mixing phosphoric acid (1.6%wt) and chromic acid (6%wt) it is molten
In liquid, at 60 c, 2 hours are placed, remove the oxide layer on ellipsoid shape aluminium flake；
(6) sine surface shape aluminium flake carries out second of anodic oxidation 8 hours in 0.3M oxalic acid solutions, and voltage is 40 volts
Spy, temperature are 5 degrees Celsius；
(7) the sine surface shape alumina wafer that (6) obtain is put into saturation mercuric chloride solution 2 hours, removes and do not aoxidize
Aluminium lamination；
(8) the sine surface shape alumina wafer deionized water rinsing obtained (7) 3-5 times；
(9) (8) are obtained into sine surface shape alumina wafer to be put into 0.1M phosphoric acid solution, 20 is placed under 30 degrees Celsius
Minute, remove barrier layer；
(10) the sine surface shape alumina wafer deionized water rinsing obtained (9) 3-5 times, dries at room temperature.
Experiment shows：
Above step is completed in the sine surface shape alumina formwork that the oxalic acid solution Anodic Oxidation of corresponding conditionses obtains
Afterwards, radial ordered arrangement is presented along sine surface vertical direction in taper hole.Near the A points shown in figure, its bellmouth edge
The minimum and maximum diameter in template surface vertical line direction is respectively：50nm and 74nm, the rate of change of nano aperture is 0.60nm/ μ
M, near the B points shown in figure, minimum and maximum diameter of its bellmouth along template surface vertical line direction is respectively：55nm and
70nm, the rate of change of nano aperture are 0.50nm/ μm, i.e., along template sinusoidal line is tangential and template surface vertical line direction, nano-pore
Aperture and varying aperture rate gradual change, can also be by changing cycle and the amplitude of anodizing time and sine surface template
The size and varying aperture rate in bellmouth aperture are adjusted, the direct observation of SEM can be with the feasible of substantive approach
Property.
Claims (1)
1. a kind of preparation method for the sine surface shape alumina formwork for preparing nano material, it is characterised in that (1) by planar shaped
High-purity aluminium flake is covered in sine surface die surface, and sine surface shape aluminium flake is obtained after forging pressing and shaping, or sinusoidal bent
Remove sine surface mould again after face mould tool surface vacuum AM aluminum metallization and obtain sine surface shape aluminium flake；(2) sine surface shape aluminium flake
4-5 minutes are polished in the ethanol and the mixed liquor of perchloric acid that volume ratio is 5: 1, voltage is 14-15 volts, and temperature is 10 Celsius
Degree；(3) aluminium flake deionized water rinsing 3-5 times is taken out；(4) sine surface shape aluminium flake is put into 0.3M oxalic acid solution Anodic oxygen
Change 20 hours, oxidation voltage is 40 volts, and temperature is 5 degrees Celsius；(5) aluminium flake that (4) obtain is put into 1: 1 mixing by volume
1.6%wt phosphoric acid and 1.6%wt chromic acid solution in, at 60 c, place 2 hours, remove ellipsoid shape aluminium flake
On oxide layer；(6) sine surface shape aluminium flake carries out second of anodic oxidation 8 hours, voltage 40 in 0.3M oxalic acid solutions
Volt, temperature are 5 degrees Celsius；(7) the sine surface shape alumina wafer that (6) obtain is put into saturation mercuric chloride solution 2 hours,
Remove unoxidized aluminium lamination；(8) the sine surface shape alumina wafer deionized water rinsing obtained (7) 3-5 times；(9) by (8)
Obtain sine surface shape alumina wafer to be put into 0.1M phosphoric acid solution, placed 20 minutes under 30 degrees Celsius, remove barrier layer；
(10) the sine surface shape alumina wafer deionized water rinsing obtained (9) 3-5 times, dries at room temperature.
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| CN114990663B (en) * | 2022-05-17 | 2024-06-07 | 山东建筑大学 | Parabolic cylindrical aluminum oxide template for preparing nano material, preparation method and application |
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| 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 |
| CN101831682A (en) * | 2010-06-09 | 2010-09-15 | 中南大学 | Method for preparing highly ordered aluminum oxide template by asymmetric two-step anodization |
| CN102041540A (en) * | 2011-01-13 | 2011-05-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Anodic aluminum oxide template with three-dimensional gradual-changed hole array nanostructure and preparation method of anodic aluminum oxide template |
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