CN106367794B - A kind of quick method for preparing orderly anodic titanium dioxide nanotube array film - Google Patents
A kind of quick method for preparing orderly anodic titanium dioxide nanotube array film Download PDFInfo
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- CN106367794B CN106367794B CN201610802199.9A CN201610802199A CN106367794B CN 106367794 B CN106367794 B CN 106367794B CN 201610802199 A CN201610802199 A CN 201610802199A CN 106367794 B CN106367794 B CN 106367794B
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Abstract
The invention discloses a kind of quick method for preparing orderly anodic titanium dioxide nanotube array film, using polished treated titanium foil as anode, using fluorine-containing solution as electrolyte, polyvinyl alcohol or polyethylene glycol is added as additive, 20 ± 5°Under the electrolysis temperature of C, constant pressure or the anodized of constant current are carried out.Using the method for the invention, it is ensured that the uniform and stable fast-growth of oxidation film can reach 1.20 μm of min without electric breakdown phenomena, the growth rate of nanotube occurs‑1More than.
Description
Technical field
The invention belongs to electrochemical technology fields, are related to a kind of preparation side of orderly anodic titanium dioxide nanotube array film
Method, and in particular to a kind of quick preparation aligned orderly, structural integrity anodic titanium dioxide nanotube array film electrochemical method.
Background technology
Titanium oxide is a kind of N-shaped semiconductor material with wide forbidden band, and energy gap is 3.0 ~ 3.2 eV, has excellent dielectric
Performance and the unique physical and chemical performance such as opto-electronic conversion, photochromic.In recent years, the technology of preparing of nano material is constantly created
Newly, titanium oxide nanotubes make because having the specific surface area and specific surface energy of bigger, better adsorption capacity and electron-transport path
It has broad application prospects in fields such as dye-sensitized solar cells, photocatalysis, ultracapacitors.And anode oxidation method
The titanium oxide nanotubes of preparation are evenly distributed, regular orderly, and by adjusting anodic oxidation condition, can facilitate control nanometer pipe range
Degree, caliber, wall thickness etc. become the effective ways for preparing titanium oxide nanotubes.
Currently, preparing the titanium oxide nanotubes of high length-diameter ratio using anodizing, ensures that its fast and stable is grown, also deposit
In very big difficulty.Such as by titanium foil in conventional fluorine-containing 1 h of electrolyte Anodic Oxidation, the TiOx nano length of tube of acquisition is only
6~15 μm (Song C B, et al., Applied Surface Science, 2014, 305: 792).When being grown
When time anodic oxidation, chemical attack effect can corrode a nanometer tube wall, cause acicular texture to appear at the top of nanotube, finally
These structure collapses form " nanometer grass ", reduce the length of nanotube, cause to extend and the growth of nanotube with oxidization time
Rate is decreased obviously.The pipe range and electrolyte component of titanium oxide nanotubes, the factors such as oxidation voltage and temperature are related.Work as nanometer
When the oxide growth of bottom of the tube and the chemical attack in tube top portion reach dynamic equilibrium, film thickness reaches highest, continues to extend oxidation
Time can not effectively increase pipe range (Macak J M, et al., Angewandte Chemie International
Edition, 2005, 44(45): 7463).Grimes etc. is contained by regulating and controlling fluorination ammonium concentration and water in ethylene glycol electrolyte
Amount makes titanium foil complete oxidation generate titanium oxide nanotubes, when concurrently increasing fluorination ammonium concentration now, need to increase water content simultaneously,
Overlength nanotube can be just obtained, and using 1 mm thickness titanium foils in room temperature（22 °C）Under, the ethylene glycol of 0.6 wt% ammonium fluorides
（Containing 3.5 vol% water）In electrolyte, 60 V anodic oxidations of constant pressure, 216 h（9 days）Prepare 1 mm long, caliber 120 nm receives
Mitron (Paulose M, et al., Journal of Physical Chemistry C, 2007,111 (41):
14992).In the ethylene glycol electrolyte of hydrofluoric acid, pass through for a long time（15 h）High pressure（120 V）Anodic oxidation can also obtain
To overlength（261 μm）Nanotube (Albu S P, et al., physica status solidi (RRL), 2007,1
(2): R65).However, the above method is long the time required to obtaining long nanotube（Such as 9 days）, this is for production application
It is not worth.In order to solve this problem it must accelerate the growth rate of titanium oxide nanotubes, and to increase nanotube growth speed
Rate must then increase the electric field in anode oxide film.But in high electric field anodic oxygen, the electrical breakdown of oxidation film easily occurs
Phenomenon causes electronic current titanium oxide nanotubes out of control to stop growing.Therefore, it is the mesh of realization titanium oxide nanotubes fast-growth
Mark, it is necessary to solve High-Field breakdown problem.
Invention content
The purpose of the present invention is to provide a kind of quick preparation aligned orderly, the anodic titanium nanotube battle arrays of structural integrity
The technology of row film.Polyvinyl alcohol or polyethylene glycol additive only need to be added, just in method using the present invention in fluorine-containing electrolyte
The fast and stable growth of the anodic titanium nanotube of aligned orderly, structural integrity may be implemented.
Realize that the technical solution of the object of the invention is：One kind quickly preparing orderly anodic titanium dioxide nanotube array film
Method using polished treated titanium foil as anode, using fluorine-containing solution as electrolyte, polyvinyl alcohol is added or polyethylene glycol adds
Add agent, 20 ± 5°Under the electrolysis temperature of C, constant pressure or the anodized of constant current are carried out.
In above-mentioned steps, the polishing treatment of titanium foil uses volume ratio 1:1:2 hydrofluoric acid, the polishing fluid of nitric acid and water composition
20 ~ 30 s of middle processing.
In above-mentioned steps, fluorine-containing solution is the ethylene glycol solution containing 0.3 wt% ammonium fluorides and 2 vol% water.
In above-mentioned steps, the polyvinyl alcohol degree of polymerization is 1200 ~ 1700, and alcoholysis degree is 78 ~ 98 %.
In above-mentioned steps, molecular weight polyethylene glycol is 700 ~ 1500.
In above-mentioned steps, polyvinyl alcohol or polyethylene glycol additive concentration are within the scope of 0.2 ~ 0.4 wt%.
In above-mentioned steps, constant pressure anodized is carried out at 120 V of high pressure.
In above-mentioned steps, constant current anodized is in 40 mA cm of current density2Lower progress.
In above-mentioned steps, using graphite cake as cathode.
Compared with prior art, the present invention its remarkable advantage is：
（1）By the way that polyvinyl alcohol or polyethylene glycol additive are added in fluorine-containing electrolyte, with oxide surface phase interaction
With, reduce occur electrical breakdown initiating electron source, to ensure oxidation film can uniform and stable fast-growth, constant pressure anodic oxygen
Change can be carried out at 120 V of high pressure, and constant current anodic oxidation can be in 40 mA cm of current density2Lower progress, and will not occur
Electric breakdown phenomena.The growth rate of oxidation film is 10 times or so under fluorine-containing electrolyte, and can be protected under Seedling height rate
Nano tube structure is held completely orderly without generating nanometer grass.
（2）An anodic oxidation only need to be carried out, and the preprocessing process of titanium foil is very simple, can be prepared into the short time
To orderly anodic titanium dioxide nanotube array film, growth rate can reach 1.20 μm of min-1More than, reach as high as 1.90
μm min-1。
（3）Electrolyte temperature uses 20 ± 5°C, within the scope of room temperature, and the fluctuation of temperature in a certain range,
The pattern of titanium oxide nanotubes is influenced little.
Description of the drawings
Fig. 1 is the constant pressure anode oxidation process current density versus time curve figure of 2 sample of comparative example.
Fig. 2 is the constant pressure anode oxidation process current density versus time curve figure of 4 sample of embodiment.
Fig. 3 is the constant current anode oxidation process voltage versus time curve figure of 8 sample of embodiment.
Specific implementation mode
Present invention is further described in detail below.
The principle of the present invention is as follows：In order to quickly prepare anodic titanium dioxide nanotube array film, it is necessary to increase anodic oxidation
Electric field in film, and the breakdown problem of oxidation film easily occurs under high field intensity, cause nanotube to stop growing.Punch-through refers to
The phenomenon that anodized insulation performance is destroyed in high electric field anodic oxygen.After water soluble polymer additive is added, electricity
Macromolecule and oxidation film surface in solution liquid have stronger interaction, reduce the defect that electrical breakdown may occur, make oxidation
Film can bear higher oxidation voltage or current density, effectively inhibit High-Field punch-through, to ensure that nanotube can be uniform
Stablize fast-growth, realizes the quick preparation of anodic titanium dioxide nanotube array film.
The present invention through the following steps that realize：
Titanium foil is immersed volume ratio 1 by step 1:1:20 ~ 30 are handled in the polishing fluid that 2 hydrofluoric acid, nitric acid and water forms
S removes the Natural Oxide Film on its surface, and the titanium foil used is high-purity titanium foil.
Step 2, the ethylene glycol solution using fluorine-containing solution i.e. containing 0.3 wt% ammonium fluorides and 2 vol% water are added as electrolyte
Polyvinyl alcohol（The degree of polymerization is 1200 ~ 1700, and alcoholysis degree is 78 ~ 98 %,）Or polyethylene glycol（Molecular weight 700 ~ 1500）Additive,
To polish titanium foil as anode, graphite cake carries out High-Field anodic oxidation, wherein additive concentration is 0.2 ~ 0.4 as cathode
Within the scope of wt%, the electrolyte temperature of High-Field anodic oxidation is controlled 20 ± 5°C, constant pressure anodic oxidation at 120 V of high pressure into
Row, constant current anodic oxidation is in 40 mA cm of current density2Lower progress.
It is further illustrated the present invention below by embodiment.
Comparative example 1
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
Constant pressure anodic oxidation reactions are carried out in fluorine-containing electrolyte, oxidation voltage is 60 V.The temperature of electrolyte passes through cryogenic liquid
Circulating pump is maintained at 20°C, anodizing time are 30 min, and anodic titanium nanotube pipe range is about：6.20 μm, caliber
About：168 nm.About 0.21 μm of min of the average growth rate of oxidation film-1。
Comparative example 2
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
Constant pressure anodic oxidation reactions are carried out in fluorine-containing electrolyte, oxidation voltage is 120 V.The temperature of electrolyte passes through cryogenic liquid
Circulating pump is maintained at 20°C, anodic oxidation reactions are very violent under high pressure, and electric current persistently rises, and anode generates a large amount of bubbles,
Oxidation film partial breakdown, interface fusing and reaction terminating, nano tube structure are also destroyed, voltage changes with time song
Line chart is shown in Fig. 1.
Embodiment 1
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.2 wt% polyethylene glycol is added in fluorine-containing electrolyte（Molecular weight 1500）, constant pressure anodic oxidation reactions are carried out, oxidation voltage is
120 V.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time are 30 min, anodic oxygen
Changing titanium nanotube pipe range is about：36.11 μm, caliber is about：171 nm.About 1.20 μm of the average growth rate of oxidation film
min-1。
Embodiment 2
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.4 wt% polyethylene glycol is added in fluorine-containing electrolyte（Molecular weight 700）, constant current anodic oxidation reactions are carried out, current density is
40 mA cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time are 30 min, sun
Pole titanium oxide nanotubes pipe range is about：39.39 μm, caliber is about：158 nm.About 1.31 μm of the average growth rate of oxidation film
min-1。
Embodiment 3
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.2 wt% polyethylene glycol is added in the electrolytic solution（Molecular weight 1000）, carry out constant current anodic oxidation reactions, current density 40
mA cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time are 30 min, anodic oxygen
Changing titanium nanotube pipe range is about：46.82 μm, caliber is about：178 nm.About 1.56 μm of the average growth rate of oxidation film
min-1。
Embodiment 4
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.2 wt% polyvinyl alcohol is added in fluorine-containing electrolyte（The degree of polymerization 1700,98 % of alcoholysis degree）, it is anti-to carry out constant pressure anodic oxidation
It answers, oxidation voltage is 120 V.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time are
30 min, anodic titanium nanotube pipe range are about：43.60 μm, caliber is about：165 nm, voltage change with time song
Line chart is shown in Fig. 2.About 1.45 μm of min of the average growth rate of oxidation film-1。
Embodiment 5
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.2 wt% polyvinyl alcohol is added in fluorine-containing electrolyte（The degree of polymerization 1700,78 % of alcoholysis degree）, it is anti-to carry out constant pressure anodic oxidation
It answers, oxidation voltage is 120 V.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time are
30 min, anodic titanium nanotube pipe range are about：40.37 μm, caliber is about：155 nm.The average growth rate of oxidation film
About 1.35 μm of min-1。
Embodiment 6
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.4 wt% polyvinyl alcohol is added in fluorine-containing electrolyte（The degree of polymerization 1200,98 % of alcoholysis degree）, it is anti-to carry out constant current anodic oxidation
It answers, current density is 40 mA cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, when anodic oxidation
Between be 30 min, anodic titanium nanotube pipe range is about：48.33 μm, caliber is about：182 nm.The average production of oxidation film
About 1.61 μm of min of rate-1。
Embodiment 7
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.2 wt% polyvinyl alcohol is added in fluorine-containing electrolyte（The degree of polymerization 1500,98 % of alcoholysis degree）, it is anti-to carry out constant current anodic oxidation
It answers, current density is 40 mA cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, when anodic oxidation
Between be 30 min, anodic titanium nanotube pipe range is about：51.55 μm, caliber is about：170 nm.The average production of oxidation film
About 1.72 μm of min of rate-1。
Embodiment 8
First by purity 99.5%, the titanium foil item of 200 μm of thickness, the cm of 6 cm × 1, volume ratio 1 is immersed:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed with deionized water dry
Only, using this titanium foil as anode, using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.
0.2 wt% polyvinyl alcohol is added in fluorine-containing electrolyte（The degree of polymerization 1700,98 % of alcoholysis degree）, it is anti-to carry out constant current anodic oxidation
It answers, current density is 40 mA cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, when anodic oxidation
Between be 30 min, anodic titanium nanotube pipe range is about：57.67 μm, caliber is about：163 nm, current density is at any time
Change curve is shown in Fig. 3.About 1.90 μm of min of the growth rate of oxidation film-1, it is 9 times of comparative example 1.
Claims (7)
1. a kind of quick method for preparing orderly anodic titanium dioxide nanotube array film, which is characterized in that after polished processing
Titanium foil be anode, using fluorine-containing solution as electrolyte, polyvinyl alcohol or polyethylene glycol additive is added, 20 ± 5°The electrolysis of C
At a temperature of, it carries out constant pressure or the anodized of constant current, polyvinyl alcohol or polyethylene glycol additive and oxide surface is mutual
Effect reduces the initiating electron source that electrical breakdown occurs, wherein constant pressure anodized is carried out at 120 V of high pressure, constant current
Anodized is in 40 mA cm of current density2Lower progress.
2. the method as described in claim 1, which is characterized in that the polishing treatment of titanium foil is to use volume ratio 1:1:2 hydrogen fluorine
20 ~ 30 s are handled in the polishing fluid of acid, nitric acid and water composition.
3. the method as described in claim 1, which is characterized in that fluorine-containing solution is containing 0.3 wt% ammonium fluorides and 2 vol% water
Ethylene glycol solution.
4. the method as described in claim 1, which is characterized in that the polyvinyl alcohol degree of polymerization be 1200 ~ 1700, alcoholysis degree be 78 ~
98 %。
5. the method as described in claim 1, which is characterized in that polyvinyl alcohol or polyethylene glycol additive concentration are 0.2 ~ 0.4
Within the scope of wt%.
6. the method as described in claim 1, which is characterized in that molecular weight polyethylene glycol is 700 ~ 1500.
7. the method as described in claim 1, which is characterized in that using graphite cake as cathode.
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| CN108546971B (en) * | 2018-05-11 | 2020-01-24 | 南京理工大学 | Method for improving binding force between anodic titanium oxide nanotube array film and titanium substrate |
| CN109338435A (en) * | 2018-12-07 | 2019-02-15 | 五邑大学 | A kind of preparation method of titania nanotube array film |
| CN109825867A (en) * | 2019-04-10 | 2019-05-31 | 东北大学 | A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array |
| CN110344097B (en) * | 2019-07-26 | 2021-04-27 | 南京理工大学 | Method for preparing anodic titanium oxide nanoflower electrode |
| CN112144088B (en) * | 2020-08-21 | 2022-03-18 | 南京理工大学 | Method for rapidly preparing anodic titanium oxide nanotube array film |
| CN113403661A (en) * | 2021-06-17 | 2021-09-17 | 中国计量大学 | Preparation method and application of titanium alloy anodic oxidation super-hydrophobic coating |
| CN113430618A (en) * | 2021-06-22 | 2021-09-24 | 江苏城乡建设职业学院 | Method for preparing porous layer of titanium dioxide |
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