CN108411346B - Anatase titania nano-tube array and its preparation method and application with (001) Solute Content in Grain - Google Patents
Anatase titania nano-tube array and its preparation method and application with (001) Solute Content in Grain Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Abstract
The invention discloses a kind of anatase titania nano-tube arrays with (001) Solute Content in Grain, the nano-tube array is made of the titanium dioxide of Detitanium-ore-type and at hexagonal array, and anatase titania nano-tube array has the preferred orientation of high energy crystal face (001).The present invention uses inexpensive, simple, easy-operating anodizing and large plastometric set method, on the pure Ni―Ti anode matrix of Ultra-fine Grained, prepare the Nano tube array of titanium dioxide of marshalling, high-sequential, the anatase titania nano-tube array in preferred orientation high energy crystal face (001) face is formed by the method for controlling pure Titanium base crystallite dimension, the transmission that the anatase titania nano-tube array has biggish specific surface area, is more advantageous to charge increases incident photon-to-electron conversion efficiency；The technologies such as large plastometric set, the anodic oxidation of use are to environment almost without any pollution.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, and in particular to one kind has the sharp of (001) Solute Content in Grain
The preparation method of titanium ore Nano tube array of titanium dioxide.
Background technique
Titanium dioxide nanotube array layer is in many fields, such as photocatalysis equipment, electronic equipment, dye sensitization of solar
Battery, light-sensitive device, sensor and bio-medical material, suffer from broad application prospect.Because of titania nanotube
Array layer structure is special, hexagonal array ordered arrangement, there is bigger ratio compared to the nanometer titanic oxide material of other forms
Surface area and stronger adsorption capacity increase incident photon-to-electron conversion efficiency conducive to the transmission of charge.
Currently, Nano tube array of titanium dioxide can be prepared there are many kinds of method, such as hydrothermal synthesis method, template, colloidal sol
Solwution method and anodizing etc..Wherein, in these methods, anodizing possesses more excellent compared to other methods
Point, such as easy to operate, low in cost, high-specific surface area, reproducible and controllability are good etc..
The performance of titanium dioxide nanotube array layer is not only related with the factors such as their pattern, size and configuration of surface；
Also there is close relationship with the crystallinity of its constituent titanium dioxide, crystal type and crystal preferred orientation.Titanium dioxide has
Three kinds of crystal structures: anatase, rutile and brockite.Wherein anatase is upper than it in the application such as solar battery, catalyst
Its both of which has embodied better performance.The crystal grain orientation on anatase surface determines its performance, such as its (101), (100)
(001) surface in face can be respectively 0.44,0.53 and 0.90J/m2。
In the prior art, the Nano tube array of titanium dioxide for generally first passing through anodic oxidation manufacture amorphousness, then leads to
It crosses subsequent annealing and obtains anatase structured titanium dioxide.But this method generally can only obtain (101) face preferred orientation
Anatase, the preferred orientation of high energy crystal face (001) can not be obtained, because (101) face is that anatase surface can be minimum, most steady
A fixed crystal face.
The common preferred orientation of anatase titania crystal is that surface can minimum, most stable of (101) face of thermodynamics.But
It is theoretical and experimental study all shows that higher (001) face of activity may be inside many applications, such as photovoltaic cell, photodegradation
Organic molecule and photocatalysis merogenesis water, serve as the main source of active site.Therefore, it is necessary to study it is a kind of it is simple to operation,
The preparation method of the economic and environment-friendly anatase titania nano-tube array with (001) Solute Content in Grain.
Summary of the invention
The present invention is 100-200nm by the crystallite dimension of the control pure Titanium base of anodic oxidation, in conjunction with subsequent anodic oxidation
And annealing operation, the anatase titania nano-tube array with high energy crystal face (001) preferred orientation is obtained, realizes titanium dioxide
Titanium nano-tube array crystal structure and preferred orientation it is controllable.
The object of the present invention is to provide a kind of simple to operation, economic and environment-friendly preparations to have (001) Solute Content in Grain
Anatase titania nano-tube array method.
The technical solution adopted by the present invention is that: one kind having the anatase titania nanometer of (001) Solute Content in Grain
Pipe array, the Nano tube array of titanium dioxide are made of the anatase titania of hexagonal arrangement, have high energy crystal face
(001) preferred orientation.
Preferably, the pure Titanium base crystallite dimension for manufacturing the anatase titania nano-tube array is 100-
200nm。
The present invention also provides the preparation sides of the anatase titania nano-tube array with (001) Solute Content in Grain
Method, comprising the following steps:
1) the pure titanium material of Ultra-fine Grained is prepared using large plastometric set method；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared；
3) amorphous Nano tube array of titanium dioxide is annealed, cooling has the rutile titania of (001) Solute Content in Grain to get arriving
Mine Nano tube array of titanium dioxide.
Preferably, the large plastometric set method is selected from high pressure torsion, isometrical channel angular extrusion, multiway forging, accumulates and fold
It rolls, continuous shear stress, cycle extrusion compress and continuously one or more of alternating bending.
Preferably, the condition control of high pressure torsion are as follows: tonnage 1-6GPa processes revolution and turns for 1-20.Further
Preferably, the condition control of high pressure torsion are as follows: tonnage 3GPa, processing revolution are 10 turns.
Preferably, the condition control of equal channel angular extrusion are as follows: the interior arc angle Φ and outer arc angle ψ of mold are 90 ° -120 °,
Head velocity is 1-25mm/s, and processing temperature is at 20-450 DEG C.It is furthermore preferred that the condition of equal channel angular extrusion controls are as follows: mold
Interior arc angle Φ and outer arc angle ψ be 100 ° -120 °, head velocity 10-20mm/s, processing temperature is at 20-450 DEG C.
Preferably, multiway forging condition control are as follows: per pass dependent variable be 20-40%, 20-450 DEG C of processing temperature.More
Preferably, multiway forging condition control are as follows: per pass dependent variable be 25-30%, 100-300 DEG C of processing temperature.
Preferably, the condition control of pack rolling is accumulated are as follows: draught per pass 15-25%, processing temperature is at 20-200 DEG C.
It is furthermore preferred that the condition control of accumulation pack rolling are as follows: draught per pass 18-20%, processing temperature is at 80-150 DEG C.
Preferably, in the pure titanium sample preparation procedure of the Ultra-fine Grained of step 1), select commercial pure titanium stick as initial sample,
Being cut into diameter is 10nm, with a thickness of the titanium sheet of 0.81-0.85mm, then carries out high pressure torsion processing.Wherein, the pressure of high pressure torsion
Power is 3GPa, and revolution is 10 turns, is carried out at room temperature.
When preparing high pressure torsion sample, pure titanium rod can be cut to diameter with the mode of wire cutting is 10nm, thickness
It for the titanium sheet of 1mm or so, is then polished with sand paper of the granularity between 400-800 mesh, before being further thinned to processing
Thickness 0.81-0.85mm, bruting process have to guarantee that upper and lower surface is parallel.
Preferably, in step 1), the crystallite dimension of the pure titanium material of Ultra-fine Grained is 100-200nm.It is furthermore preferred that step 1)
In, the crystallite dimension of the pure titanium material of Ultra-fine Grained is 120-150nm.
Preferably, in step 2), the electrolyte that anodizing uses includes following components in percentage by weight: 0.25-
0.75wt.% ammonium fluoride, 1-10wt.% deionized water and 89.5-98.75wt.% alcohols solvent.
Preferably, alcohols solvent is selected from one or both of glycerine and ethylene glycol, the i.e. electricity of anodizing use
Solving liquid includes following components in percentage by weight: 0.25-0.75wt.% ammonium fluoride, 1-10wt.% deionized water and 89.5-
98.75wt.% glycerine；Or electrolyte includes following components in percentage by weight: 0.25-0.75wt.% ammonium fluoride, 1-
10wt.% deionized water and 89.5-98.75wt.% ethylene glycol.
It is furthermore preferred that the electrolyte that anodizing uses includes following components in percentage by weight: 0.25wt.% fluorination
Ammonium, 1wt.% deionized water and 98.75wt.% glycerine.
Preferably, in step 2), amorphous Nano tube array of titanium dioxide, anodizing are prepared using anodizing
In, anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is exposed to as anode, the pure titanium material surface of Ultra-fine Grained
Area in electrolyte is the border circular areas that diameter is 5-8mm, and pure titanium is as cathode, electrode distance 0.8-2cm.More preferably
, the area of Ultra-fine Grained pure titanium material surface exposure in the electrolytic solution is the border circular areas that diameter is 6mm, pure titanium as cathode,
Electrode distance is 1cm.
Preferably, in step 2), anodizing is divided into two steps, and first step anodic oxidation 14- is first carried out at 25-35V
Then the TNT array layer of manufacture is successively used adhesive tape and ultra sonic machinery to remove, then carries out second at 25-35V by 18h
Walk anodic oxidation 5-8h.
It is furthermore preferred that first carrying out first step anodic oxidation 16h at 30V, then the TNT array layer of manufacture is successively used
Adhesive tape and ultra sonic machinery removing, then second step anodic oxidation 6h is carried out at 30V.
It is further preferred that before the anodic oxidation for carrying out step 2), first successively by the surface of the pure titanium material of Ultra-fine Grained
Polish via the sand paper of 800,1200,2500 and 4000 mesh, then successively the suspension of 3,1 and 0.25 μm of aluminium oxide into
Row polishing, then successively ultrasound 8-30 minutes in acetone, ethyl alcohol and deionized water.
Preferably, it in step 3), by amorphous Nano tube array of titanium dioxide in air atmosphere, is moved back at 300-400 DEG C
Fiery 0.5-2h, annealing are completed, and 20-25 DEG C of cooled to room temperature is to get to the anatase two with (001) Solute Content in Grain
Titania nanotube array.
The present invention also provides the anatase titania nano-tube arrays with (001) Solute Content in Grain to urge as light
Change the application of device, dye-sensitized solar cells, light-sensitive device, sensor component and battery storage materials.Anatase dioxy
Change the transmission that titanium nano-tube array has biggish specific surface area, is conducive to charge, increases incident photon-to-electron conversion efficiency, therefore can make
For photocatalytic device, light-sensitive device, sensor component, adsorbent material and battery storage materials.
Compared with prior art, the present invention uses inexpensive, simple, easy-operating anodizing and large plastometric set side
Method prepares the Nano tube array of titanium dioxide of marshalling, high-sequential, passes through control on the pure Ni―Ti anode matrix of Ultra-fine Grained
The method for making pure Titanium base crystallite dimension forms high energy preferred orientation (001) anatase titania nano-tube array, the rutile titania
The transmission that mine Nano tube array of titanium dioxide has biggish specific surface area, is more advantageous to charge increases incident photon-to-electron conversion efficiency；It adopts
The technologies such as large plastometric set, anodic oxidation are to environment almost without any pollution.
Detailed description of the invention
Fig. 1 is metallographic microscope photo (the metallographic microscope model: Olympus BX41M- of pure titanium sample before high pressure torsion
LED), crystallite dimension is about 33 ± 5 μm；
Fig. 2 is transmission electron microscope photograph via bright field (the transmission electron microscope instrument type of pure titanium sample after high pressure torsion
Number: JEM3010, acceleration voltage 300kV), crystallite dimension is about 135 ± 10nm；
Fig. 3 is the transmission electron microscope dark field photo of pure titanium sample after high pressure torsion, crystallite dimension is about 135 ±
10nm；
Fig. 4 is the transmission electron microscope selection electronic diffraction photo of pure titanium sample after high pressure torsion, selective electron diffraction
Spot is circlewise；
Fig. 5 is Nano tube array of titanium dioxide SEM sectional view, with a thickness of 2051nm；
Fig. 6 is Nano tube array of titanium dioxide SEM dorsal view, and the hexagonal arrangement of nanotube, bottom surface tube diameters are
55nm；
Fig. 7 is the ultra-fine Titanium base after Ultra-fine Grained Titanium base, anodic oxidation and titanium dioxide nanotube array layer above
The X ray diffracting spectrum after titanium dioxide nanotube array layer annealing with the ultra-fine Titanium base after anodic oxidation and above；
Fig. 8 be coarse-grain Titanium base, the coarse-grain Titanium base after anodic oxidation and titanium dioxide nanotube array layer above and
Coarse-grain Titanium base after anodic oxidation and the X ray diffracting spectrum after titanium dioxide nanotube array layer annealing above.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The invention discloses a kind of preparation sides with the anatase titania nano-tube array of (001) crystal face preferentially
Method, the preparation method include the following steps: 1) to obtain the pure titanium material of Ultra-fine Grained using severe Plastic Deformation Methods；2) this super
Amorphous Nano tube array of titanium dioxide is manufactured by anodic oxidation on the pure titanium surface of fine grain；3) then by next in air gas
Annealing in atmosphere is had the Anatase polycrystalline structure Nano tube array of titanium dioxide of (001) Solute Content in Grain.
Embodiment 1
The preparation method of anatase titania nano-tube array with (001) Solute Content in Grain, including following step
It is rapid:
1) use high pressure torsion preparation crystallite dimension for the pure titanium material of the Ultra-fine Grained of 140nm；
In the pure titanium sample preparation procedure of Ultra-fine Grained of step 1, selects commercial pure titanium stick as initial sample, be cut into diameter
For 10nm, then thickness carries out high pressure torsion processing in the titanium sheet of 0.81-0.85mm, wherein the pressure of high pressure torsion is
3GPa, revolution are 10 turns, are carried out at room temperature；Crystallite dimension is about 140nm after high pressure torsion；
When preparing high pressure torsion sample, pure titanium rod can be cut into diameter with the mode of wire cutting is 10nm, thickness
It for the titanium sheet of 1mm or so, is then polished with sand paper of the granularity between 400-800 mesh, before being further thinned to processing
Thickness 0.81-0.85mm guarantees that the upper and lower surface of titanium sheet is parallel；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, first by the surface of the pure titanium material of Ultra-fine Grained successively via 800,1200,2500 and 4000 purposes
Sand paper is polished, and is then successively polished in 3,1 and 0.25 μm of aluminum oxide suspensions, then successively in acetone, ethyl alcohol and go
Ultrasound 8 minutes in ionized water；
Anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is as anode, the pure titanium material of Ultra-fine Grained
The area of surface exposure in the electrolytic solution is the border circular areas that diameter is 5mm, and pure titanium is as cathode, electrode distance 0.8cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.25wt.% ammonium fluoride, 1wt.%
Deionized water and 98.75wt.% glycerine；
Anodizing is divided into two steps, first step anodic oxidation 16h is first carried out at 30V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 6h is carried out at 30V；
3) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 1h at 350 DEG C, and annealing is completed, natural
20-25 DEG C is cooled to room temperature to get the anatase titania nano-tube array with (001) Solute Content in Grain is arrived.
Wherein, before high pressure torsion the MIcrosope image of pure titanium sample as shown in Figure 1, crystallite dimension is about after high pressure torsion
140nm, as shown in the transmission electron microscope image of Fig. 2-4.
As seen in figs. 5-6, wherein Fig. 5 is dioxy to the scanning electron microscope pattern of anatase titania nano-tube array
Change titanium nano-tube array SEM sectional view, Nano tube array of titanium dioxide is titania nanotube with a thickness of 2051nm, Fig. 6
Array SEM dorsal view, the bottom surface tube diameters of Nano tube array of titanium dioxide are 55nm.
Fig. 7 is the ultra-fine Titanium base after Ultra-fine Grained Titanium base, anodic oxidation and titanium dioxide nanotube array layer above
The X ray diffracting spectrum after titanium dioxide nanotube array layer annealing with the ultra-fine Titanium base after anodic oxidation and above；Fig. 8
After the coarse-grain Titanium base after coarse-grain Titanium base, anodic oxidation and titanium dioxide nanotube array layer and anodic oxidation above
Coarse-grain Titanium base and above titanium dioxide nanotube array layer annealing after X ray diffracting spectrum.By Fig. 7 and Fig. 8 it is found that sun
The X-ray map of pole oxidation front and back all only has the peak of Titanium base, illustrates the titania nanotube battle array generated after anodic oxidation
It is classified as non crystalline structure.After annealing, it is anatase structured that Fig. 8 shows that amorphous titanium dioxide array is converted into, on coarse crystal
(101) peak in face shows maximum intensity, shows that it has (101) preferred orientation；And Fig. 7 be shown in it is sharp on Ultra-fine Grained matrix
The peak in titanium ore (004) face shows maximum intensity, shows that it has the preferred orientation in (001) face.
Embodiment 2
The preparation method of anatase titania nano-tube array with (001) Solute Content in Grain, including following step
It is rapid:
1) use high pressure and torsion preparation crystallite dimension for the pure titanium material of the Ultra-fine Grained of 120nm；
In the pure titanium sample preparation procedure of Ultra-fine Grained of step 1, selects commercial pure titanium stick as initial sample, be cut into diameter
For 10nm, then thickness carries out high pressure torsion processing in the titanium sheet of 0.81-0.85mm, wherein the pressure of high pressure torsion is
5GPa, revolution are 12 turns, are carried out at room temperature；
When preparing high pressure torsion sample, pure titanium rod can be cut into diameter with the mode of wire cutting is 10nm, thickness
It for the titanium sheet of 1mm or so, is then polished with sand paper of the granularity between 400-800 mesh, before being further thinned to processing
Thickness 0.81-0.85mm guarantees that the upper and lower surface of titanium sheet is parallel；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, first by the surface of the pure titanium material of Ultra-fine Grained successively via 800,1200,2500 and 4000 purposes
Sand paper is polished, and is then successively polished in 3,1 and 0.25 μm of aluminum oxide suspensions, then successively in acetone, ethyl alcohol and go
Ultrasound 10 minutes in ionized water；
Anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is as anode, the pure titanium material of Ultra-fine Grained
The area of surface exposure in the electrolytic solution is the border circular areas that diameter is 6mm, and pure titanium is as cathode, electrode distance 0.8cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.5wt.% ammonium fluoride, 2wt.%
Deionized water and 97.5wt.% ethylene glycol；
Anodizing is divided into two steps, first step anodic oxidation 15h is first carried out at 28V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 6h is carried out at 28V；
3) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 2h at 300 DEG C, and annealing is completed, natural
20-25 DEG C is cooled to room temperature to get the anatase titania nano-tube array with (001) Solute Content in Grain is arrived.
Embodiment 3
The preparation method of anatase titania nano-tube array with (001) Solute Content in Grain, including following step
It is rapid:
1) use isometrical channel angular extrusion method preparation crystallite dimension for the pure titanium material of the Ultra-fine Grained of 110nm；
In the pure titanium sample preparation procedure of Ultra-fine Grained of step 1, selects commercial pure titanium stick as initial sample, be cut into diameter
For 10nm, then thickness carries out isometrical channel angular extrusion processing, wherein isometrical channel corner in the titanium sheet of 0.81-0.85mm
The condition of extruding controls are as follows: the interior arc angle Φ and outer arc angle ψ of mold are 90 ° -120 °, using Bc processing route, head velocity
For 10mm/s, processing temperature is 300 DEG C；
When preparing isometrical channel angular extrusion sample, cutting length is 10cm, and diameter is the pure titanium sample of pole of 10mm；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, first by the surface of the pure titanium material of Ultra-fine Grained successively via 800,1200,2500 and 4000 purposes
Sand paper is polished, and is then successively polished in 3,1 and 0.25 μm of aluminum oxide suspensions, then successively in acetone, ethyl alcohol and go
Ultrasound 12 minutes in ionized water；
Anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is as anode, the pure titanium material of Ultra-fine Grained
The area of surface exposure in the electrolytic solution is the border circular areas that diameter is 6mm, and pure titanium is as cathode, electrode distance 0.8cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.3wt.% ammonium fluoride, 5wt.%
Deionized water and 94.7wt.% glycerine；
Anodizing is divided into two steps, first step anodic oxidation 18h is first carried out at 30V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 6h is carried out at 30V；
3) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 1h at 350 DEG C, and annealing is completed, natural
20-25 DEG C is cooled to room temperature to get the anatase titania nano-tube array with (001) Solute Content in Grain is arrived.
Embodiment 4
The preparation method of anatase titania nano-tube array with (001) Solute Content in Grain, including following step
It is rapid:
1) use multiway forging method preparation crystallite dimension for the pure titanium material of the Ultra-fine Grained of 150nm；
In the pure titanium sample preparation procedure of Ultra-fine Grained of step 1, selects commercial pure titanium stick as initial sample, be cut into diameter
For 10nm, then thickness carries out multiway forging processing in the titanium sheet of 0.81-0.85mm, wherein the condition of multiway forging, which controls, is
Per pass dependent variable be 40%, 20 DEG C of processing temperature；
When preparing multiway forging sample, the sample of a height of 10 × 10 × 15mm of length and width is cut with wire cutting；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, first by the surface of the pure titanium material of Ultra-fine Grained successively via 800,1200,2500 and 4000 purposes
Sand paper is polished, and is then successively polished in 3,1 and 0.25 μm of aluminum oxide suspensions, then successively in acetone, ethyl alcohol and go
Ultrasound 8-15 minutes in ionized water；
Anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is as anode, the pure titanium material of Ultra-fine Grained
The area of surface exposure in the electrolytic solution is the border circular areas that diameter is 8mm, and pure titanium is as cathode, electrode distance 1.5cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.6wt.% ammonium fluoride, 6wt.%
Deionized water and 93.4wt.% glycerine；
Anodizing is divided into two steps, first step anodic oxidation 14h is first carried out at 32V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 7h is carried out at 32V；
3) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 1.2h at 380 DEG C, and annealing is completed, from
It is cooled to room temperature 20-25 DEG C so to get the anatase titania nano-tube array with (001) Solute Content in Grain is arrived.
Embodiment 5
The preparation method of anatase titania nano-tube array with (001) Solute Content in Grain, including following step
It is rapid:
1) use high pressure and torsion preparation crystallite dimension for the pure titanium material of the Ultra-fine Grained of 180nm；
In the pure titanium sample preparation procedure of Ultra-fine Grained of step 1, selects commercial pure titanium stick as initial sample, be cut into diameter
For 10nm, then thickness carries out high pressure torsion processing in the titanium sheet of 0.81-0.85mm, wherein the pressure of high pressure torsion is
1GPa, revolution are 10 turns, are carried out at room temperature.
When preparing high pressure torsion sample, pure titanium rod can be cut into diameter with the mode of wire cutting is 10nm, thickness
It for the titanium sheet of 1mm or so, is then polished with sand paper of the granularity between 400-800 mesh, before being further thinned to processing
Thickness 0.81-0.85mm guarantees that the upper and lower surface of titanium sheet is parallel；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, first by the surface of the pure titanium material of Ultra-fine Grained successively via 800,1200,2500 and 4000 purposes
Sand paper is polished, and is then successively polished in 3,1 and 0.25 μm of aluminum oxide suspensions, then successively in acetone, ethyl alcohol and go
Ultrasound 30 minutes in ionized water；
Anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is as anode, the pure titanium material of Ultra-fine Grained
The area of surface exposure in the electrolytic solution is the border circular areas that diameter is 6mm, and pure titanium is as cathode, electrode distance 1.6cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.75wt.% ammonium fluoride, 8wt.%
Deionized water and 91.25wt.% ethylene glycol；
Anodizing is divided into two steps, first step anodic oxidation 16h is first carried out at 35V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 6h is carried out at 35V；
3) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 2h at 350 DEG C, and annealing is completed, natural
20-25 DEG C is cooled to room temperature to get the anatase titania nano-tube array with (001) Solute Content in Grain is arrived.
Embodiment 6
The preparation method of anatase titania nano-tube array with (001) Solute Content in Grain, including following step
It is rapid:
1) use accumulation pack rolling method preparation crystallite dimension for the pure titanium material of the Ultra-fine Grained of 200nm；
In the pure titanium sample preparation procedure of Ultra-fine Grained of step 1, selects commercial pure titanium stick as initial sample, be cut into diameter
For 10nm, then thickness carries out accumulation pack rolling processing in the titanium sheet of 0.81-0.85mm, wherein accumulates the condition control of pack rolling
Are as follows: draught per pass 15-25%, processing temperature is at 100 DEG C；
It is thick using 1mm to accumulate pack rolling sample, the Titanium board material of 200 × 300mm；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, the titanium sheet of 10 × 10mm is cut from accumulation pack rolling sample, then by the pure titanium material of Ultra-fine Grained
Surface successively polish via the sand paper of 800,1200,2500 and 4000 mesh, then successively in 3,1 and 0.25 μm of aluminium oxide
Suspension is polished, then successively ultrasound 15 minutes in acetone, ethyl alcohol and deionized water；
Anodic oxidation device uses dual electrode cell, and the pure titanium material of Ultra-fine Grained is as anode, the pure titanium material of Ultra-fine Grained
The area of surface exposure in the electrolytic solution is the border circular areas that diameter is 8mm, and pure titanium is as cathode, electrode distance 2cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.75wt.% ammonium fluoride,
9.25wt.% deionized water and 90wt.% ethylene glycol；
Anodizing is divided into two steps, first step anodic oxidation 18h is first carried out at 35V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 8h is carried out at 35V；
3) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 2h at 400 DEG C, and annealing is completed, natural
20-25 DEG C is cooled to room temperature to get the anatase titania nano-tube array with (001) Solute Content in Grain is arrived.
Comparative example 1
The preparation method of anatase titania nano-tube array, comprising the following steps:
1) using common pure titanium material as matrix, amorphous Nano tube array of titanium dioxide is prepared using anodizing；
Before anodic oxidation, first by the surface of common pure titanium material successively via the sand of 800,1200,2500 and 4000 mesh
Paper is polished, and is then successively polished in 3,1 and 0.25 μm of aluminum oxide suspensions, then successively acetone, ethyl alcohol and go from
Ultrasound 8 minutes in sub- water；
Anodic oxidation device uses dual electrode cell, and as anode, surface is exposed to common pure titanium material
Area in electrolyte is the border circular areas that diameter is 5mm, and pure titanium is as cathode, electrode distance 0.8cm；
The electrolyte that anodizing uses includes following components in percentage by weight: 0.25wt.% ammonium fluoride, 1wt.%
Deionized water and 98.75wt.% glycerine；
Anodizing is divided into two steps, first step anodic oxidation 16h is first carried out at 30V, then by the TNT array of manufacture
Layer is successively removed using adhesive tape and ultra sonic machinery, then second step anodic oxidation 6h is carried out at 30V；
2) by amorphous Nano tube array of titanium dioxide in air atmosphere, anneal 1h at 350 DEG C, and annealing is completed, natural
It is cooled to room temperature 20-25 DEG C, obtains the anatase titania nano-tube array of low energy (101) Solute Content in Grain.
Wherein, the crystallite dimension of common pure titanium material used in step 1) is about 33 μm, as shown in Figure 1.It is prepared
The anatase titania nano-tube array with low energy (101) Solute Content in Grain XRD spectrum such as the coarse-grain titanium in Fig. 8
Shown in the XRD spectrum of matrix anode post-oxidation anneal, the peak in (101) face is shown on coarse crystal, shows that it has (101)
Preferred orientation.
Claims (8)
1. the anatase titania nano-tube array that one kind has (001) Solute Content in Grain, which is characterized in that the nanometer
Pipe array is made of the titanium dioxide of Detitanium-ore-type and at hexagonal array, and anatase titania nano-tube array has high energy
The preferred orientation of crystal face (001), the crystallite dimension for manufacturing pure Titanium base used in the anatase titania nano-tube array are
100-200nm。
2. the preparation side of the anatase titania nano-tube array described in claim 1 with (001) Solute Content in Grain
Method, which comprises the following steps:
1) the pure titanium material of Ultra-fine Grained is prepared using large plastometric set method, the crystallite dimension of the pure titanium material of Ultra-fine Grained is 100-
200nm；
2) using the pure titanium material of Ultra-fine Grained as matrix, amorphous Nano tube array of titanium dioxide is prepared；
3) amorphous Nano tube array of titanium dioxide is annealed to get the anatase titanium dioxide with (001) Solute Content in Grain is arrived
Titanium nano-tube array.
3. preparation method according to claim 2, which is characterized in that the large plastometric set method be selected from high pressure torsion, etc.
One of diameter channel angular extrusion, multiway forging, accumulation pack rolling, continuous shear stress, cycle extrusion compression and continuous alternating bending
Or it is several.
4. preparation method according to claim 3, which is characterized in that the condition of high pressure torsion controls are as follows: tonnage is
1-6GPa processes revolution and turns for 1-20；The condition of isometrical channel angular extrusion controls are as follows: the interior arc angle Φ and outer arc angle Ψ of mold
It is 90 ° -120 °, head velocity 1-25mm/s, processing temperature is 20-450 DEG C；The condition of multiway forging controls are as follows: per pass
Secondary dependent variable is 20-40%, and processing temperature is 20-450 DEG C；Accumulate the condition control of pack rolling are as follows: draught per pass 15-
25%, processing temperature is 20-200 DEG C.
5. preparation method according to claim 2, which is characterized in that in step 2), prepare amorphous using anodizing
Nano tube array of titanium dioxide, the electrolyte that anodizing uses includes following components in percentage by weight: 0.25-
0.75wt.% ammonium fluoride, 1-10wt.% deionized water and 89.5-98.75wt.% alcohols solvent.
6. preparation method according to claim 5, which is characterized in that in step 2), in anodizing, anodic oxygen makeup
It sets using dual electrode cell, the pure titanium material of Ultra-fine Grained is as anode, the face of the pure titanium material surface exposure of Ultra-fine Grained in the electrolytic solution
Product is the border circular areas that diameter is 5-8mm, and pure titanium is as cathode, electrode distance 0.8-2cm.
7. preparation method according to claim 5, which is characterized in that in step 2), anodizing is divided into two steps, first exists
First step anodic oxidation 14-18h is carried out under 25-35V, and the TNT array layer of manufacture is successively then used into adhesive tape and ultrasonic wave
Mechanical stripping, then second step anodic oxidation 5-8h is carried out at 25-35V.
8. the anatase titania nano-tube array described in claim 1 with (001) Solute Content in Grain is urged as light
Change the application of device, dye-sensitized solar cells, light-sensitive device, sensor component and battery storage materials.
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