CN109338435A - A kind of preparation method of titania nanotube array film - Google Patents
A kind of preparation method of titania nanotube array film Download PDFInfo
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- CN109338435A CN109338435A CN201811495409.XA CN201811495409A CN109338435A CN 109338435 A CN109338435 A CN 109338435A CN 201811495409 A CN201811495409 A CN 201811495409A CN 109338435 A CN109338435 A CN 109338435A
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- 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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Abstract
The invention discloses a kind of preparation method of titania nanotube array film, include the following steps: that (1) cuts the pure titanium sheet of 10mm × 20mm, polish through abrasive paper for metallograph, successively with acetone, ethyl alcohol, deionized water ultrasonic cleaning；(2) to pure titanium sheet polishing treatment 30s pretreated pure titanium sheet is made, three kinds of liquor capacity ratios are 1:4:5 in the mixed solution then formed with hydrofluoric acid, concentrated nitric acid, deionized water；(3) at room temperature, it is put into oxidation solution using as the pure titanium sheet of pretreatment of anode and as the graphite flake of cathode, oxidation processes 30s~3000s under the voltage environment of 20V, the orderly high density titania nanotube array film of pure titanium Surface Creation compound with regular structure are provided using D.C. regulated power supply；Electrode spacing between the anode and cathode is 3cm, and oxidation solution includes the electrolyte of 0.5wt% hydrofluoric acid, 0.1wt% glacial acetic acid and the mixing of 0.1wt% polyethylene glycol, the polyethylene glycol as the glacial acetic acid of complexing agent, as stabilizer.
Description
Technical field
The present invention relates to the technical field of film of Nano tube array preparation process more particularly to a kind of titania nanotube arrays
The preparation method of film.
Background technique
It is well known that the microstructure of substance is largely fixed the functionality of material, nano wire, is received nanometer rods
The structures such as mitron have obtained extensive research.TiO2It is a kind of important inorganic functional material, in the storage and benefit of solar energy
With, photoelectric conversion, photocatalytic degradation etc. have a wide range of applications.Nanotube has bigger than nano-powder, nanometer film
Specific surface area, higher surface property are expected to improve TiO2Photoelectric conversion and photocatalysis efficiency.TiO at present2The preparation of nanotube
Method has template, hydro-thermal method and anodizing.Relative to first two method, anodic oxidation, which has, does not need template, preparation
The advantages that simple process, low in cost, product are convenient for recycling.Traditional anodizing is that TiO is prepared in titanium substrate2Nanometer
Pipe array films, however the preparation process complexity of conventional oxidation titanium film is cumbersome, the film of Nano tube array for reacting generation is different in a jumble,
It is not monolithically formed overall structure orderly, nanotube growth is unstable and different in size, and the density of nanotube is more low, makes oxygen
Changing titanium film, there are many defects in generating process.
Summary of the invention
The purpose of the invention is to overcome the above-mentioned prior art, a kind of titania nanotube array film is provided
Preparation method, the preparation method of the titania nanotube array film is using anodizing in hydrofluoric acid, glacial acetic acid, polyethylene glycol
Pure titanium Surface Creation caliber about 50-70nm, pipe range about 500-600nm compound with regular structure are orderly in aqueous solution TiO2 nanometers of high density
Pipe array films, preparation method is simple, facilitates operation, easy to accomplish, and TiO2 nano-tube array film density obtained is high, structure
It is regular orderly, it generates and stablizes, length is consistent, and mechanical structure is also stable.
The technical solution adopted by the present invention to solve the technical problems is: a kind of preparation side of titania nanotube array film
Method includes the following steps:
(1) the pure titanium sheet for cutting 10mm × 20mm, polishes through abrasive paper for metallograph, successively with acetone, ethyl alcohol, deionized water ultrasound
Cleaning；
(2) pure titanium sheet polishing treatment 30s is made in the mixed solution then formed with hydrofluoric acid, concentrated nitric acid, deionized water
Pretreated pure titanium sheet, three kinds of liquor capacity ratios are 1:4:5；
(3) at room temperature, it is put into oxidation solution using as the pure titanium sheet of pretreatment of anode and as the graphite flake of cathode,
Oxidation processes 30s~3000s under the voltage environment of 20V is provided using D.C. regulated power supply, pure titanium Surface Creation compound with regular structure has
The high density titania nanotube array film of sequence；
Electrode spacing between the anode and cathode is 3cm, and oxidation solution includes 0.5wt% hydrofluoric acid, 0.1wt%
The electrolyte of glacial acetic acid and the mixing of 0.1wt% polyethylene glycol, the polyethylene glycol as the glacial acetic acid of complexing agent, as stabilizer.
Further, the pure titanium sheet purity in the step (1) is 99.6%, with a thickness of 200 μm.
Further, the molecular weight of the polyvinyl alcohol in the step (2) is 20000.
Further, the caliber of the high density titania nanotube array film is 50-70nm, pipe range 500-
600nm。
The titania nanotube array film forming process is as follows: originally, titanium surface quickly forms fine and close oxidation film, oxidation
The generation of film carries out simultaneously with dissolution, and early period, generating rate was faster than rate of dissolution, and the double electrical layers of Cathode/Solution Interface are (tight
Close layer/dispersion layer), make oxidation film Surface Creation aperture, adjacent aperture integrates increasing hole, then forms tubule,
Tubule further incorporates bigger pipe, and after aperture reaches maximum, nanotube pipe range also will continue to increase, into stablizing growth step
Section.Ultimately form the orderly high density film of Nano tube array of compound with regular structure.
In conclusion the preparation method of titania nanotube array film of the invention using anodizing hydrofluoric acid,
Pure titanium Surface Creation caliber about 50-70nm, pipe range about 500-600nm compound with regular structure are orderly in glacial acetic acid, Aqueous Solutions of Polyethylene Glycol
High density TiO2 film of Nano tube array, preparation method is simple, facilitates operation, easy to accomplish, and TiO2 nanotube obtained
Array film density is high, and compound with regular structure is orderly, generates and stablizes, length is consistent, and mechanical structure is also stable.
Detailed description of the invention
Fig. 1 is pure titanium anode oxidation process current versus time curve figure in a solution of hydrofluoric acid；
Fig. 2 is the SEM figure that pure titanium oxidation film after aoxidizing 30s is in a stage in Fig. 1；
Fig. 3 is the SEM figure that pure titanium oxidation film after aoxidizing 300s is in b-stage in Fig. 1；
Fig. 4 is the SEM figure that pure titanium oxidation film after aoxidizing 600s is in the c stage in Fig. 1；
Fig. 5 is the SEM figure that pure titanium oxidation film after aoxidizing 1000s is in the d stage in Fig. 1；
Fig. 6 is that pure titanium oxidation film after aoxidizing 1200s is in the side in d stage and surface SEM figure in Fig. 1；
Fig. 7 is that pure titanium oxidation film after aoxidizing 1600s is in the side in d stage and surface SEM figure in Fig. 1；
Fig. 8 is that pure titanium oxidation film after aoxidizing 2200s is in the side in d stage and surface SEM figure in Fig. 1；
Fig. 9 is that pure titanium oxidation film after aoxidizing 3000s is in the side in d stage and surface SEM figure in Fig. 1；
Figure 10 is the TiO in anode oxidation process2Nanometer pipe range-time plot；
Figure 11 is metal/solution interface double electrical layers figure.
Specific embodiment
Embodiment 1
A kind of preparation method of titania nanotube array film, includes the following steps: described in the present embodiment 1
(1) the pure titanium sheet for cutting 10mm × 20mm, polishes through abrasive paper for metallograph, successively with acetone, ethyl alcohol, deionized water ultrasound
Cleaning；
(2) pure titanium sheet polishing treatment 30s is made in the mixed solution then formed with hydrofluoric acid, concentrated nitric acid, deionized water
Pretreated pure titanium sheet, three kinds of liquor capacity ratios are 1:4:5；
(3) at room temperature, it is put into oxidation solution using as the pure titanium sheet of pretreatment of anode and as the graphite flake of cathode,
Oxidation processes 30s~3000s under the voltage environment of 20V is provided using D.C. regulated power supply, pure titanium Surface Creation compound with regular structure has
The high density titania nanotube array film of sequence；
Electrode spacing between the anode and cathode is 3cm, and oxidation solution includes 0.5wt% hydrofluoric acid, 0.1wt% ice vinegar
The electrolyte of acid and the mixing of 0.1wt% polyethylene glycol, the polyethylene glycol as the glacial acetic acid of complexing agent, as stabilizer.
In the present embodiment, the pure titanium sheet purity in the step (1) is 99.6%, with a thickness of 200 μm.
In the present embodiment, the molecular weight of the polyvinyl alcohol in the step (2) is 20000.
In the present embodiment, the caliber of the high density titania nanotube array film is 50-70nm, pipe range 500-
600nm。
The titania nanotube array film forming process is as follows: originally, titanium surface quickly forms fine and close oxidation film, oxidation
The generation of film carries out simultaneously with dissolution, and early period, generating rate was faster than rate of dissolution, and the double electrical layers of Cathode/Solution Interface are (tight
Close layer/dispersion layer), make oxidation film Surface Creation aperture, adjacent aperture integrates increasing hole, then forms tubule,
Tubule further incorporates bigger pipe, and after aperture reaches maximum, nanotube pipe range also will continue to increase, into stablizing growth step
Section.Ultimately form the orderly high density film of Nano tube array of compound with regular structure.
Fig. 1 is pure titanium anode oxidation process current versus time curve figure in a solution of hydrofluoric acid, is had from the I-t curve of Fig. 1
Four Main Stages, the characteristics of reflecting oxide growth: a stage indicates one layer of fine and close high resistance of titanium Surface Creation after being powered
The barrier layer oxidation film of value；The rising of b-stage electric current is the generation due to oxidation film surface micropore, and constantly fusion generation is bigger
Hole, caused by the decline of titanium oxide resistance；The rising of c stage current slows down, and belongs to nanotube caliber fusing stage, d stage current size
It is held essentially constant, belongs to film of Nano tube array steady growth developing stage.Thin film of titanium oxide is colorless and transparent substance, when titanium table
When face generates after oxidation film illumination on the surface under anodic oxidation condition, the light being reflected back from titania surface can be with transmission
Film reaches the reflected light rays encounter interference effect again of titanium-based bottom surface, so that the titanium surface being oxidized be made to show interference
Color.In anode oxidation process early period, oxidation film generating rate is greater than rate of dissolution, and oxide thickness is continuously increased, different thick
The oxidation film layer of degree has an impact the refraction and reflection of luminous flux, light, and different colors is formed by interference effect.?
There is the change procedure of purple-blue-yellow-reddish brown (optical wavelength is sequentially increased) in 30s -300s period oxidation film color,
Titanium oxide nanotubes have been formed when 800s, and film surface appearance has very big change at this time, mainly based on the diffusing reflection of light,
Color is silver gray, and the color of period hereafter, titanium surface are held essentially constant.
The current versus time curve figure of comparative diagram 1, Fig. 2 are in the current versus time curve a stage, and titanium surface is quickly generated densification
Oxidation film；Fig. 3 is in current versus time curve b-stage initial stage, and micropore occurs in oxidation film surface；Fig. 4 is in current-vs-time song
Line c stage, titanium oxide nanotubes have been formed, and adjacent tubule incorporates mutually other side, gradually form stable big pipe.At Fig. 5
In the current versus time curve c later period in stage, the fusion process of nanotube terminates substantially.
For the d stage (pipe range developing stage) for preferably analyzing current versus time curve figure, the nanotube formed to the d stage
Array films have carried out surface and side Shape measure.Fig. 6, Fig. 7, Fig. 8 and Fig. 9 are in 0.5wt%HF+ glacial acetic acid+poly- second respectively
The SEM figure of the side and surface of oxidation film after 1200s, 1600s, 2200s, 3000s is aoxidized in glycol solution respectively.
In Fig. 6, Fig. 7, Fig. 8 and Fig. 9 in corresponding four times chosen, nanometer pipe diameter size is basicly stable, explanation
The d stage starts nanotube caliber and has basically reached maximum on current versus time curve figure, and the fusing stage of tubule is completed.?
In the length variation of film of Nano tube array, four time points upper length be respectively as follows: 240.1nm, 341.7nm, 435.1nm,
521.1nm, as Figure 10 anode oxidation process in TiO2Nanometer pipe range-time plot, it can be seen that with the progress of time
Pipe range increases, and generating rate is in reduction trend.
The reaction that pure titanium sheet occurs in anode oxidation process is mainly made of following two step:
Ti+2H2O-4e→TiO2+4H+ (1)
TiO2+6F-+4H+→[TiF6]2-+2H2O (2)。
As shown in Figure 11, in Cathode/Solution Interface, there is two kinds of interphase interactions: one is electrodes and solution two
Electrostatic interaction caused by residual charge in phase；Another kind is that various particles in electrode and solution are (ion, solute molecule, molten
Agent molecule etc.) between short distance effect, such as Characteristic Adsorption, dipole orientations arrangement, it is only in several nanometers of zero point of distance
Interior generation.Two kinds of interphase interactions make Cathode/Solution Interface, and there is double electrical layers, due to free electron in metal phase
Concentration is very big, it is believed that whole residual charges are all tight distributions in metal, constitute close layer；In solution side, due to solution
Concentration is smaller, constitutes dispersion layer under electrostatic interaction and the effect of the contradiction of particle warm-up movement.
The spacing very little of two charge layers of Cathode/Solution Interface, field strength is very big, and titanium surface is made to be quickly generated fine and close oxygen
Change film, since solution interface is dispersion layer, causing oxidation film, there are non-uniform generations on Nano grade, and titanium oxide is non-
Crystalline state, thin film of titanium oxide can have many defects in generating process, with the increase of oxide thickness, thin film of titanium oxide two
The voltage of end load increases, and after voltage reaches certain value, random breakdown occurs for the oxidation film of existing defects, generates aperture.With
The generation of aperture, electric current have rising by a small margin, constantly there are the generation and dissolution on new barrier layer, adjacent aperture collection in this stage
At increasing hole, tubule is then formed, tubule further incorporates bigger pipe, until caliber increases to maximum, mechanics knot
Structure is stablized, and becomes smaller in the fusing stage electric current ascensional range of pipe, concentration, the anodic oxidation voltage of the final size of caliber and electrolyte
It is related.After caliber increases to maximum, pipe range is in stable build phase, as barrier layer generating rate reaches with rate of dissolution
Balance, ultimately forms the orderly high density film of Nano tube array of compound with regular structure, length about 500-600nm.
The above described is only a preferred embodiment of the present invention, not making any form to technical solution of the present invention
On limitation.According to the technical essence of the invention any simple modification to the above embodiments, equivalent variations and repair
Decorations, in the range of still falling within technical solution of the present invention.
Claims (4)
1. a kind of preparation method of titania nanotube array film, which comprises the steps of:
(1) the pure titanium sheet for cutting 10mm × 20mm, polishes through abrasive paper for metallograph, successively clear with acetone, ethyl alcohol, deionized water ultrasound
It washes；
(2) pre- place is made to pure titanium sheet polishing treatment 30s in the mixed solution then formed with hydrofluoric acid, concentrated nitric acid, deionized water
The pure titanium sheet of reason, three kinds of liquor capacity ratios are 1:4:5；
(3) at room temperature, it is put into oxidation solution, uses using as the pure titanium sheet of pretreatment of anode and as the graphite flake of cathode
D.C. regulated power supply provides oxidation processes 30s~3000s under the voltage environment of 20V, and pure titanium Surface Creation compound with regular structure is orderly
High density titania nanotube array film；
Electrode spacing between the anode and cathode is 3cm, and oxidation solution includes 0.5wt% hydrofluoric acid, 0.1wt% ice vinegar
The electrolyte of acid and the mixing of 0.1wt% polyethylene glycol, the polyethylene glycol as the glacial acetic acid of complexing agent, as stabilizer.
2. a kind of preparation method of titania nanotube array film according to claim 1, which is characterized in that the step
(1) the pure titanium sheet purity in is 99.6%, with a thickness of 200 μm.
3. a kind of preparation method of titania nanotube array film according to claim 2, which is characterized in that the step
(2) molecular weight of the polyvinyl alcohol in is 20000.
4. a kind of preparation method of titania nanotube array film according to claim 3, which is characterized in that the height
The caliber of density titania nanotube array film is 50-70nm, pipe range 500-600nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113046812A (en) * | 2021-02-09 | 2021-06-29 | 佛山市安齿生物科技有限公司 | Anodic oxidation liquid for titanium alloy dental abutment system and preparation method and application thereof |
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| CN105780084A (en) * | 2014-12-18 | 2016-07-20 | 天津城建大学 | Preparation method of long-pipe diameter TiO2 nanotube array and application of long-pipe diameter TiO2 nanotube array |
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105780084A (en) * | 2014-12-18 | 2016-07-20 | 天津城建大学 | Preparation method of long-pipe diameter TiO2 nanotube array and application of long-pipe diameter TiO2 nanotube array |
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
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| CN113046812A (en) * | 2021-02-09 | 2021-06-29 | 佛山市安齿生物科技有限公司 | Anodic oxidation liquid for titanium alloy dental abutment system and preparation method and application thereof |
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